Dispersive Kinetics

job:L0434J 9-7-1998 page:1 colour:0
4 Dispersive kinetics
By ANDRZEJ PLONKA
Institute of Applied Radiation Chemistry, Technical University of Lodz,
Wroblewskiego 15, 93-590 Lodz, Poland
1 Introduction
Rate processes for which many timescales coexist are called dispersive, cf. the presenta-
tion by Scher et al. of dispersive transport and relaxation, and the authors account`
of the development of dispersive chemical kinetics. Dispersive rate processes are
endemic in condensed media.`
`
The rate coecient for a dispersive process depends on time. In the case of a
chemical reaction, the time dependence of the rate coecient, k(t), termed the specic
reaction rate, was rationalized in the following way.` Reactions by their very nature
have to disturb reactivity distributions of the reactants in condensed media, as the
more reactive species are the rst ones to disappear from the system. The extent of this
disturbance depends on the ratio of the rates of reactions to the rate of internal
rearrangements (mixing) in the system restoring the initial distribution in reactivity of
reactants. If the rates of chemical reactions exceed the rates of internal rearrangements,
then the initial distributions in reactant reactivity are not preserved during the course
of reactions and the specic reaction rates depend on time. If, however, the rates of
internal rearrangements exceed markedly the rates of chemical reactions, then the
extent of disturbance is negligible and classical kinetics, with a constant specic
reaction rate, k, termed the reaction rate constant, may be valid as an approximation.
The reason is that the distribution in reactivity is only seen when it is changing during
the reaction course: otherwise it is summed additively to yield a single timescale.`
The above picture provides a proper ground to present in Section 2 a number of
recently developed comprehensive models of dispersive kinetics and to quote some
recent discussions on the basic concepts of kinetics. Kinetics in condensed media is
hard to separate from transport and relaxation. In Section 3 some common features of
dispersive rate processes in condensed media are discussed. Mathematical models, as
clearly recognized by Bajzer et al.,' are ideas, and thus are limited only by logic and
imagination. The extent to which models conform to reality is determined by testing
them against experimental data with the aid of computational and statistical methods.
This is done in Section 4 for uids, in Section 5 for solids, and in Section 6 for some
heterogeneous systems. Conclusions comprising Section 7 reect to some extent the
authors personal point of view and interest, which undoubtedly may also be seen in
89
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the choice of the subject matter from this rapidly developing interdisciplinary eld of
research.
2 Phenomenological aspects of dispersive kinetics
In the stochastic model of reaction kinetics in renewing environments, discussed in
detail in a previous report,` the structural reorganization of the host matrix was
included by imposing upon the static disorder model the additional assumption that at
randominstants reinitialization occurs. Reinitialization consists of a random reassign-
ment of guest hopping rates, with the values having the same initial distribution. At the
molecular level almost all condensed-phase systems are disordered. In a three-dimen-
sional disorder system, without renewals, the number of distinct sites, S(t), visited by a
random walker is sublinear in time
S(t) (t/
"
)?, 0 : 1 (1)
where
"
is scaling the time and the dispersion parameter : is that proper to account for
the static aspects of disorder. Renewals are described by the fractal set of renewal
moments following from the use of Kohlrauschs function
u(t) exp[ (t/t
"
)@], 0 [O1 (2)
to describe the internal rearrangements in the system. In eqn. (2) t
"
denotes the
eective relaxation time and [ is the dispersion parameter for relaxation.
Averaging S(t) given by eqn. (1) over the renewal sequences following from relation
(2) one gets
S(t),(t/
"
)
:
(3)
where the dispersion parameter : to be observed experimentally is given by
: 1 (1 :)(1[) (4)
and time is scaled by the weighted geometrical mean of timescales for a random walk
(
"
) and relaxation (t
"
)
"
:/:
"
t'
:/:
'
"
(5)
The specic reaction rate for highly reactive species, i.e. for those with local reaction
probability (when two reactants collide) P;1, is given by
k(t) b
dS(t),
dt
(6)
where b denotes the volume of site (cell) visited by the random walker. From eqn. (3)
and (6) one gets for k(t)
k(t)/(dm`/mol) (:/
"
)(t/
"
)
:
(7)
To obtain the limit of classical kinetics, i.e. the constant specic reaction rate, one has
to use the long-time approximation, t t
"
, of Kohlrauschs relaxation function (2)
with [1. This yields : 1, cf. eqn. (4), and then from eqn. (7)
k
"
(8)
90 A. Plonka
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with
"
?
"
t'?'
"
(9)
For decreasing local reaction probability P below the value of one, the dispersion
parameter : quickly attains unity, and therefore one nally gets
k
"
(10)
the constant specic reaction rate of classical kinetics. On the other hand, to obtain the
limit of suppressed renewals one has to put, quite formally, [ 0 into eqn. (4), which
yields : : and
k (:/
"
)(t/
"
)O (11)
[cf. eqn. (5) and (7)].
Reaction path
In classical kinetics, the concept of an energy prole along a reaction path helps us to
visualise the main features of a chemical reaction, including its mechanism. Along the
reaction path, the reactants are separated from the products by a potential energy
barrier. Constant specic reaction rates are related to thermally activated over-barrier
transitions (Arrhenius,` Eyring,` Kramers") or to quantum-mechanical tunnelling
through the barrier (Gamov," Gurney and Condon). For a constant specic reac-
tion rate a single potential energy barrier is envisaged for the reaction course.
As recently discussed by Wang and Wolynes,` since the rst half of the century
there have been many studies aimed toward a mathematical description of barrier
crossing processes in condensed-phase systems; cf. the developments in variational
transition state theory in condensed media reported by Tucker.` When the timescale
of the environmental uctuations is short compared to the time of the overall rate
processes, the eect of the environment on the barrier crossing is merely to renormal-
ize the rate coecient. This might be seen from eqn. (8) and (9). However, there are
many cases, such as electron transfer in viscous solvents, reactions in biomolecules and
glasses, and femtosecond events in uid environments, where the uctuations of the
environment are slower than or comparable in timescale to the overall barrier cross-
ing. In this situation the traditional theory of chemical kinetics breaks down. Concen-
trating on the slowmode, one can study this problemusing a diusional description, cf.
the recent studies of Drozdov and Talkner" on thermally activated escape processes
in a double well coupled to a slow harmonic mode, or discussion of reaction-coordi-
nate-dependent friction in classical activated barrier crossing dynamics presented by
Haynes and Voth.` The diusional approach is most appropriate` when the envi-
ronmental uctuations relax exponentially. In many typical slow-uctuating environ-
ments such as glasses, viscous liquids, and biomolecules, multiexponential relaxations
are normally observed. In this situation, the diusion equation approach to the
environment, while capturing much of the spirit of the phenomena, may quantitatively
fail. Wang and Wolynes'` studied the reaction dynamics in a slowly uctuating
environment where relaxation follows a stretched exponential law, i.e. Kohlrauschs
relaxation function (2), using a path integral method. In general, however, the path
integrals involved in reaction dynamics are not exactly evaluable, and one must resort
to approximate methods to nd the dominant survival paths. This was seen` to be the
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analogue of semiclassical methods in quantum mechanics or steepest descent ap-
proaches in conventional statistical mechanics. Dominant survival paths satisfy a
variational equation of motion. This equation balances the probability of an environ-
mental uctuation in the absence of the reaction with the changes of survivability
along a path. If the rate constant depends only weakly on the environmental variable
the survival path follows the ordinary relaxation to equilibrium. If the rate coecients
vary rapidly with environmental variables, the dominant survival paths, however,
exhibit more complex behaviour. Many phenomena familiar from geometrical optics
are seen. These include reection o rapid variation in the rate constant, as well as
refraction, giving paths very dierent from the equilibrium relaxation forms.
It was mentioned` that the steepest descent method can be inaccurate in certain
situations. The example was considered where there exists a relatively small range of
values of the environmental parameter corresponding to high reaction rates. The
dominant survival path is produced by the balance between the tendency of the
environmental uctuations to relax to the equilibrium and the tendency to avoid the
high-rate regions in order to survive. This situation is not entirely stable. Occasionally
there can be large-amplitude uctuations from the balanced position quickly entering
and coming out of the high-rate region, if the region is small in size. This uctuation
will contribute signicantly to the rate process, and may be as signicant as the
dominant path. In the long-time limit, there can be many of these types of uctuations
which can contribute signicantly to the changes of population. These uctuations are
very similar to instantons in imaginary-time quantum mechanics, which have the
physical interpretation there of quantum tunnelling. An instanton approach, used by
Smerdarchina et al.` to describe the dynamics of molecular inversion, is based on the
observation that for temperatures that are low compared to the barrier height the
eective tunnelling trajectories are conned to a narrow region in conguration space,
since the tunnelling amplitude depends exponentially on the barrier. This implies that
tunnelling retains many of the characteristics of a one-dimensional process, dominated
by a path of least resistance. This path, known as the instanton-bounce path, satises
the classical equations of motion in a potential obtained by turning the barrier
upside-down.
Wang and Wolynes` have given a general calculation for a rate process in a slowly
uctuating environment including the instanton path contributions. A frequency-
dependent rate coecient naturally emerges when taking into account the interactions
between instantons, which represent the long-time memory of the environment. When
the instanton interactions are ignored, a single-exponential decay law is recovered. It
was seen that the survival probability is increased due to the contribution from
instantons. A detailed example was worked out for a slowly uctuating environment
with stretched exponential relaxation and a piecewise linear dependence of rate on the
environmental coordinate. However, the explicit forms of k(t) were not given.
The hopping of a moving particle over an activation barrier with a Markovian
uctuating height was investigated by Vlad and Mackey" by assuming that the
process is characterizedby two characteristic timescales: the minimumhopping time t
"
corresponding to zero activation energy and the regression timescale t
''
of the uctu-
ations of the activation energy. The moments lK(t),, m0 of the uctuating survival
function l(t) at time t as well as the average probability of the passage time +(t) were
evaluated by taking into account all contributions of the dierent paths of the
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activation energy E(t'), t Pt' P0. The survival statistics obey a fractal scaling law only
if the regression of the uctuations is lower than the hopping process. In this case a
statistical fractal behaviour emerges for the time interval t
''
t t
"
for which
lK(t),:t&, +(t) :t'>&', where 1 PH0 is a positive fractal exponent. For
larger times t t
''
the survival statistics are exponential: +(t), lK(t),:exp( t/t
''
).
The condition t
''
t
"
denes a non-ideal statistical fractal for which self-similarity
exists only in the time window t
''
t t
"
; for larger times t t
''
the tail of the
probability density +(t) is exponential, and thus the moments of the passage time are
nite. In the limit t
''
;- the ideal statistical fractal behaviour of the static random
activation energy model is recovered: the uctuations of the activation energy barrier
are frozen, the tails of the functions lK(t), and +(t) are self-similar up to innity, and
the moments of the passage time are innite. It is shown that the uctuations of the
energy barrier increase the eciency of the hopping processes. The results are extended
to non-Markovian uctuation dynamics for which o1/t
''
is a random rate selected
from a generalized PorterThomas distribution. In this case the passage over the
barrier is even more ecient. The hopping occurs with certainty in a nite time interval
of a given length t
. At the end of the interval the moments lK(t), of the survival

function l(t) collapse to zero.
Comparing this approach with some other recent treatments of the passage over a
uctuating energy barrier the authors" conclude that until now the study of uctuat-
ing energy barriers has focused mainly on a certain type of resonance phenomenon,
such as stochastic resonance or resonant activation. The starting point of these
approaches is a one- or two-dimensional FokkerPlanck equation which describes the
passage over the barrier. The FokkerPlanck equation is integrated by assuming that
the barrier height has known stochastic properties. These approaches are of course
more appropriate from the statistical mechanical point of view; they are generaliz-
ations of the classical Kramers theory of activated processes." In contrast, Vlad and
Mackey" take the Arrhenius equation for granted and assume that the corresponding
activation energy is a random function of time with known stochastic properties.
Although from the theoretical point of view the validity of such an assumption is
questionable, it has been shown in the literature of random activation energy models
that for static disorder it is consistent with experimental data for a large class of natural
phenomena, cf. Vlad and Mackey" and references therein.
See also Makarov and Topaler`" on non-Poisson statistics of reactive events and
non-exponential kinetics. For stochastic description of chain reaction see Vlad and
Mackey.` The same group of authors have given the stochastic model for time- and
space-dependent coloured noise,`` and have investigated the cooperative behaviour of
interacting Le vy ights.`` For reactive ux formalism for activated rate processes, see
Bader et al.`"
Grifoni et al.`` have studied stochastic resonance in the temperature range where
quantumtunnelling corrections to the classical rate of activationare relevant. Stochas-
tic resonance occurs in nonlinear dynamical systems where the response to a weak
coherent input is enhanced by the presence of noise. For a particle subjected to
moderate-to-large friction, it was shown that semiclassical stochastic resonance can be
enhanced considerably by quantum uctuations, as compared to the predictions of a
classical analysis. In contrast to the eect of stochastic resonance, resonant activation
may occur when the potential is subjected to deterministic oscillation.`' Reimann``
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has investigated the mean escape time for thermal diusion in a uctuating metastable
potential. A new type of resonant activation (a minimumin the mean escape time as a
function of the correlation time of the potential uctuations) was predicted analyti-
cally, explained in simple terms, and conrmed numerically. In its pure form it
generically occurs for potentials without uctuations near the barrier and the well. The
eect is dominated by a minimum in the exponentially leading Arrhenius factor at a
correlation time that stays nite for asymptotically small thermal and potential
uctuations.
Nonlinear systems in the presence of noise can show quite counterintuitive dynam-
ics. Stochastic resonance and resonant activation are seen by Mantegna and Spa-
gnolo`` as paradigmatic examples. These authors have observed the noise-enhanced
stability of an unstable system by investigating the escape times from a time-
modulated metastable physical system. In their system the height of the well barrier
was periodically modulated. The modulation could be so intense that the height of the
well barrier could be negligible or completely absent for a short time; i.e. the system
might be deterministically stable overall or unstable overall depending on the strength
of the modulating signal. By investigating a deterministically overall-unstable system
they observed that the maximumof the average escape time fromthe well is for a nite
value of the noise intensity.
An exact solution of the mean exit time problem for a free inertial process driven by
Gaussian white noise was obtained by Masoliver and Porra;`" spectra, exit times and
long-time asymptotics in the zero-white-noise limit were analysed by Mathieu.`"
Escape and response times of double-barrier heterostructures were analysed by Dietze
and Darling.` Resonant tunnelling through two discrete energy states was reported
by van der Vaart et al.`` Figielski`` has proposed a conceptual experiment which
allows one to dene the time taken for a particle to traverse a region with arbitrary
potential prole under quasi-stationary conditions. A mathematical representation
was used to examine the electron tunnelling time through a rectangular potential
barrier. It was found that in the transparent-barrier limit the electron traverses the
barrier quasi-ballistically, whereas in the opaque-barrier limit the tunnelling time rises
exponentially with the barrier width. Jung and Mayer-Kress`" have presented the rst
numerical evidence that in an excitable mediumthe synchronizationof spatiotemporal
patterns with external excitatory waves shows a sharp peak at a nite, well dened
noise level independent of the system size. This eect can be understood as a generaliz-
ation of the concept of stochastic resonance to spatially extended systems. Wargitsch
and Hu bler`` have shown that nonlinear oscillators have a large response to special
aperiodic driving forces. The scaling theory of bifurcations in the symmetric weak-
noise escape problem has been discussed by Maier and Stein.`' Freilikher et al.`` have
reported on enhanced transmission of classical waves due to disorder.
The dynamics of a particle that interacts with its environment constitutes a basic
problem in physics, cf. Cohen`` and references therein. Localization due to space
structure, rather than due to randomness, was discussed by Wang,`" and exact results
were presented for a Sierpinski gasket. The localization due to randomness was
thought`" to be well understood. It was recalled that in his seminal paper in 1958
Anderson"" pointed out that electronic wavefunctions in a random potential may be
profoundly altered if the randomness is suciently strong. He demonstrated, by using
a simplied theoretical model, that a wavefunction may become localized when the
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disorder, due to the presence of impurities or imperfections in the lattice, is strong.
Generally speaking, in a quantum system, there are both tunnelling and interference
eects within a wavefunction scattered by a random potential. These two aspects can
aect each other and produce rich physics. Delocalized states, such as the Bloch states
in perfect crystals, appear when the tunnelling of particles (with certain energies) is
enhanced by a constructive interference of these waves. On the other hand, when the
interference is destructive, it may lead to a localization of the state. For example,
phases of electron waves in disordered systems will be randomized due to scattering by
impurities. The interference of the scattered waves is destructive if the disorder is
strong enough. This leads to localization in disordered systems. However, it is very
dicult to determine quantitatively (or sometimes even qualitatively) whether an
electronic state is localized or extended (delocalized) for a given disordered system. Del
Rio et al." have examined various issues relevant to localization in the Anderson
model. They have shown that there is more to localizationthan exponentially localized
states by presenting an example with such states but for which x(t)`,/t`B is un-
bounded for any o 0 (see Section 3). For an Anderson transition in a model of
coupled random polymer chains see Zambetaki et al.,"` for an Anderson transition in
conjugated polymers see Markos and Evangelou;"` for an Anderson transition and
energy-level statistics see Katomeris and Evangelou"" and Evangelou and Kat-
sanos;"` for diusion of electrons in two-dimensional disordered symplectic systems,
i.e. systems with a spin-dependent interaction having the time reversal symmetry, see
Kawarabayashi and Ohtsuki."' For symplectic ensembles, as well as for orthogonal
ensembles (systems with time reversal and spin rotation symmetry) and unitary
ensembles (systems without time reversal symmetry) the second moment of the wave
packet r`(t), at the Anderson transition was shown to behave as :t?, with : 2/3, by
Ohtsuki and Kawarabayashi."` For localization of electrons, fractons and random
walks in random fractals see also Bunde and Dra ger"` and Bunde et al."" Instan-
taneous normal mode analysis was used by Bembenek and Laird`" and Laird and
Bembenek` to discuss the role of localization in glasses and supercooled liquids.
Energy proles
For a time-dependent specic reaction rate the potential energy barrier has to evolve
in time. Taking the most familiar Arrhenius picture to relate
"
from eqn. (7) to the
activation energy E
by
"
""
exp(E
/RT) (12)
(where
""
denotes the temperature-independent pre-exponential factor, T is tempera-
ture and R is the gas constant) one nds that the form (7) of k(t) implies`` the
time-dependent activation energy E(t) given by
E(t) E
(1 :)ln(t/
"
) (13)
in units of RT.
At a rst glance at relation (13) one might be worried by the limit E(t) ;- for
t ;0. A somewhat similar problem was encountered by Montroll and Bendler,`` and
it was concluded that no serious decay of reactants starts until t is a signicant fraction
of
"
. Besides, there are nite mean values ln(t/
"
), and higher moments of the
distribution of logarithms of lifetime for all schemes of elementary reactions.`" From
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these moments one obtains the moments of activation energy distributions during the
reaction course
(E(t) E
)L, (1 :)LlnL(t/
"
), (14)
For further discussion, two kinetic schemes are of importance: rst-order (or
pseudo-rst-order) kinetics and second-order equal-concentration kinetics.
First-order kinetics
The rst-order kinetic equation with k(t) given by eqn. (7) reads
c/c
"
exp[ (t/
"
)
:
] (15)
Rewriting the survival probability given by eqn. (15) as
c/c
"
exp exp[:ln(t/
"
)] (16)
one gets for the distribution of logarithms of lifetimes, ln(t/
"
), the mean value
ln(t/
"
),/: (17)
and the variance
D`[ln(t/
"
)] `/6:` (18)
where denotes the Euler constant. Then, recalling relation (14) one gets
E(t) E
1
1
:
(19)
and
D`[E(t) E
]
`
6
1
:
1
`
(20)
For the limit of classical kinetics, : ;1, one gets E(t),E
and D`[E(t) E
] 0.
The kinetic equation (15) is identical, in mathematical form, with Kohlrauschs
relaxation function (2). For : ;: it might be physically acceptable to represent eqn.
(15) in the form of a Laplace transform
exp[ (t/
"
)?
`
"
f (k)exp( kt)dk, or
(21) `
"
g()exp( t/)d
for g() f (1/)`, and to interpret eqn. (15), like Kohlrauschs relaxation function (2)
in some applications, in terms of the superposition of monoexponential decays distrib-
uted continuously with density given by f (k) or g(). For a probabilistic analysis of the
form of f (k), leading to u(t) given by eqn. (2), see Weron`` and Jurlewicz and Weron.`'
It follows from eqn. (21) that the density of f (k) can be found as an inverse Laplace
transformof the left-hand side of eqn. (21). Although the inverse transforms are known
exactly only for the numerical values of : equal to 1/3, 1/2 and 2/3, there is no problem
with other numerical values of :. A number of approximate algorithms have been
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proposed```'
' to evaluate f (k) numerically, in addition to a representation of f(k) in

terms of a convergent series given by Pollard.'` Furthermore, for checking and
application purposes, Dishon et al.'` published tables, accurate to six gures, of f (k)
for a number of values of : between 0.25 and 0.999. The problem is that f(k) is the
density of a stable distribution with no moments.'" This lack of moments of f (k),
together with the time dependence of the rate coecient for stretched exponential
decay, were always seen as a disadvantage in this kind of interpretation of experimen-
tal results tted with Kohlrauschs relaxation function. However, for cases when there
are reasons to believe that the distribution of lifetimes displayed by Kohlrauschs
relaxation function originates from a prior distribution of monoexponential decays, it
is worth noting that there are moments of g() for 1/k. Furthermore, these
moments are directly related to those of g(t) following from eqn. (15)
tL,n!L, (22)
The moments of g(t), which are easy to calculate directly from eqn. (15), are given by
(t/
"
)L,I(1 n/:) (23)
where I denotes the gamma function. Because of eqn. (22) and (23) one has
(/
"
)L, (1/n!)I(1 n/:) (24)
cf. Weron`` and Lindsey and Paterson.``
Even more remarkable is the existence of the moments for g(ln ) and their simple
relationship to those of g(ln t)
lnt, ln, (25)
and
D`(lnt) D`(ln)
`
6
(26)
Comparing eqn. (17) and (25) one nds
ln(/
"
),
1
1
:
(27)
and comparing eqn. (18) and (26) one gets
D`(ln/
"
)
`
6
1 :`
:
(28)
Finally, assuming that the Arrhenius relations hold for monoexponential decays,
and denoting by E() the respective activation energies, one gets from eqn. (27)
E() E
D
,
1
1
:
(29)
i.e. exactly what one is given by eqn. (19). From eqn. (28), however,
D`[E() E
D
]
`
6
1 :`
:`
(30)
and this variance is greater than the variance given by eqn. (20). The dierence is
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D`[E(t) E
D
] D`[E() E
D
]
`
3
1
:
1
(31)
This dierence, reecting the specicity of interpretation of eqn. (15) in terms of
Laplace transform (21), turns to zero not only for : ;1 (for local reaction probability
P;0, cf. above) but also, as is easy to check from the ratio of variances, for : ;0.
Second-order equal-concentration kinetics
The second-order equal-concentration kinetic equation, with k(t)/c
"
given by the
right-hand side of eqn. (7), reads
c/c
"
[1 (t/
"
)
:
] (32)
with the asymptote
c/c
"
:t
:
, t ;- (33)
to be much discussed below.
Rewriting eqn. (32) as
c/c
"
1 exp[:ln(t/
"
)] (34)
one nds
ln(t/
"
),0 (35)
D`[ln(t/
"
)] `/3:` (36)
Then, recalling relation (14), one gets
E(t) E
,0 (37)
D`[E(t) E
]
`
3
(1 :)`
:`
(38)
Here, independently of the numerical value of :, E(t),E
, and for : ;0
D`[E(t) E
] 0. Also, independently of the numerical value of : one has, cf. eqn.

(35), lnt, ln
. This is true despite t, - from eqn. (32), and one might be

worried about Po lyas'` rule of non-zero asymptotic escape probability for a random
walker in a three-dimensional system.
Recently, the diusion-limited reactions AA;A and AA;0 in dimension
d 2 were reconsidered by Alemany'' from the point of view of the random-walk
theory. It was pointed out that Po lyas theorem on the returning probability of a
random walker to the origin, which would imply a probability less than one for the
meeting of two typical particles, would predict the possibility of a state in which the
reaction seems to have to cease spontaneously. This is in contradiction with the very
well known asymptotic N(t) :t, i.e. eqn. (22) for : 1, for the particle populations
of these reactions. In fact, a given condition was presented, in which the relative
particle number N(t)/N(0) decays to a non-vanishing constant. The condition is that
the initial distribution of particles in d-dimensional space has a dimension , such that
0 d 2.
In analogy to eqn. (21) one can write for the second-order equal-concentration
kinetic equation (32)
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1
1(t/
"
)?
"
g()
1 t/
d (39)
from which one gets
g()
sin(:)
(/
"
)?
(/
"
)`? (/
"
)? cos(:) 1
(40)
and for : ;0 one has g() o(
"
) and g() attains maximum at
"
. There are
no moments of g() given by eqn. (40). Also there are no moments for (t/
"
) from the
left-hand side of eqn. (39). There are moments of the distribution of logarithms of
lifetimes
ln t,ln, (41)
D`(lnt) D`(ln) `/3 (42)
If the Arrhenius relation holds for any one gets
g(E)
sin(:)
expA
exp2A2 cos(:)expA1
(43)
for A:(EE
D
) and
E(),E
D
(44)
which is exactly what was obtained from eqn. (37) and
D`[E() E
D
]
`
3
1 :`
:`
(45)
Comparing eqn. (45) and (38) one nds
D`[E(t) E
D
] D`[E() E
D
]
2`
3
1
:
1
(46)
and once again we see the dierence discussed above for rst-order kinetics. For the
dependence of activation energy on the degree of conversion see also Budrugeac and
Segal.'`'`
The phenomenological approach to kinetics with k(t) has been compared with that
in which the kinetics with a time-dependent specic reaction rate is interpreted in
terms of a superposition of classical patterns. This approach might be useful, however,
only at extremely low temperatures, cf. Berlin.'" The signicance of temperature-
dependent distributions of activation energies is discussed by Halpern.`" For a dis-
cussion on nding the barrier height distribution see Straub and Choi,` Zwanzig``
and Straub et al.`` Struik`" comments on the physical meaning of so-called apparent
activation energy, and Flynn`` discusses the use and abuse of the so-called tempera-
ture integral in thermal analysis.
In the above discussion a simple Arrhenius picture was used. For a history of the
temperature dependence of the reaction rate in the development of reaction kinetics
see Flynn.`` In addition to convenience, there is also a theoretical justication for the
application of the Arrhenius equation to the kinetics of solid-state reactions. Here it
seems proper to quote Galwey and Brown,`' who indicate that no realistic alternative
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to the Arrhenius equation capable of expressing the form of the k vs. T relationship or
providing an explanation of this pattern of behaviour has gained acceptance. Addi-
tional constants have been introduced, e.g.
lnk ab/Tcln TdT (47)
but these, as already described by Laidler,`` are theoretically sterile in that the
constants do not lead to a deeper understanding of the mechanisms of chemical
reactions. This is seconded by Tu dos and David,`` who discussed weak points in the
Eyring theory and its application. First, the parameters of the two equations are
mathematically convertible with each other. Thus Eyrings conceptual quantities
(entropy and enthalpy) give no new physical information. Secondly, the Eyring theory
postulates an equilibrium for the activated state. However, in the case of processes in
which change is an inherent characteristic, this assumption seems to be unjustied.
Depending on the specic property under discussion, the Arrhenius equation may
equivalently refer to a specic reaction rate, as above, to inverse response time t,
inverse viscosity p, frequency f, d.c. conductivity o
, etc. In numerous cases, es-

pecially in the supercooled regime of liquids, the characteristic relaxation times refuse
to follow the Arrhenius equation over a substantial range of temperatures. This is the
case reported by Stickel et al.,`" who have measured the dielectric relaxation times of
the :-process of phenyl salicylate (salol) covering the frequency range 10`10" Hz.
Salol is a representative of the class of low-molecular-weight organic glass-forming
materials, and the highly resolved temperature dependence of its dynamics fails to
follow the common routes for rationalizing dynamics. These routes included the
Arrhenius equation, the VogelFulcherTamman (VFT) equation`"
``
t t
"
exp[ B/(TT
"
)] (48)
and therefore the equivalent WilliamsLaudelFerry (WLF) relation,`` the relations
proposed by Bendler and Shlesinger`"
t :exp[ B/(TT
"
)``] (49)
Binder and Young``
t :exp( B/T") (50)
Richert and Ba ssler`'
t :exp( B/T`) (51)
Souletie and Bertrand``
t :[(TT
)/T]A, 0 (52)
and that put forward by Go tze and Sjo gren``
t :[(TT
)/T
]A :(TT
)A, 0 (53)
However, Stickel et al.`" did observe VFT behaviour within the limits 265320 K, i.e.
for temperatures ranging fromsignicantly above the glass transition at T
220 K to
far above the melting point.
As discussed in the previous report,` the slowing down of relaxation processes with
temperature decrease culminates in a glass-transition region. Therefore, well belowthe
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glass transition one may expect to be close to the limit given by eqn. (11), and on
increasing the temperature toward the glass transition one may expect to approach the
limit of classical kinetics given by eqn. (8) and (9). Furthermore, if both processes, i.e.
guest movement and host matrix relaxation, are thermally activated, with e.g. activa-
tion energies E
D
and E
O
, then the activation energy E
should approach E
:E
t
in
the low-temperature limit and E
::E
(1 :)E
O
in the high-temperature limit.
This was found to be the case in numerous systems" with E
O
E
D
. Here we have to
note that we are entering the region in which the extrapolations of the WLF equation,
or the equivalent VFT equation, are not valid.
Compensation law
Moura Ramos et al.`" have analysed the physical signicance of the so-called compen-
sation law, which consists of a linear relationship between the logarithm of the
pre-exponential factor of the Arrhenius equation and the apparent activation energy.
This might be deduced from eqn. (9). In terms of the Eyring equation of the rate theory
the compensation lawcan be described as a linear relationship between AS
and AH
.
For some early examples see Exner.""
According to Moura Ramos et al.`" this behaviour can be purely artefactual, the
linear dependence of entropy vs. enthalpy being a consequence of a statistic compensa-
tion pattern that arises solely from experimental errors. On the other hand, the
compensation behaviour may in many cases reveal a real physical behaviour, and this
seems to be the case for some relaxation mechanisms in polymeric materials studied by
thermal stimulation techniques. For a process with a single relaxation time the
temperature dependence of t can be described by the Arrhenius equation written as
t t
"
exp
kT
(54)
where t
"
is the pre-exponential factor and E
the apparent activation energy. If the

compensation behaviour is observed, there is a concomitant increase of t
"
and E
so
that the Arrhenius lines converge to a single point of coordinates t
and T
such that
t
"
t
exp
kT
(55)
Substitution of eqn. (55) into eqn. (54) gives
t t
exp
k
1
T
1
T
(56)
which is the well known compensation equation. On the other hand, according to the
Eyring equation`
t
h
kT
exp
AS
k
exp
AH
kT
(57)
where AS
and AH
are, respectively, the entropy and the enthalpy of activation. The

pre-exponential factor in the Arrhenius equation is directly related to the activation
entropy. For a process with a single relaxation time, the representation of ln(tT) vs.
1/T (the so-called Eyring plot) gives a straight line whose slope is related to AH
and
whose intercept is related to AS
. If the compensation behaviour is observed, the

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Eyring lines of the dierent thermal sampling experiments will converge to the com-
pensation point. As the temperature of the thermal sampling experiments increases,
the activation enthalpy and the activation entropy increase concomitantly, and the
temperature of the compensation point, T
, is the slope of the plot of AH
vs. AS
. The
physical signicance of the compensation point and of the compensation behaviour is
far from being elucidated. It was concluded`" that the compensation behaviour is a
feature of cooperative relaxations, including glass transitions in polymeric materials,
but it is not characteristic of many relaxations observed above and belowT
. Compen-
sation is a result of the sharp increase of AH
as one approaches T
from the
low-temperature side (which is equivalent to a concomitant increase of AH
and AS
with increasing temperature) and it is characterized by a compensation point. It was

demonstrated that the compensation temperature, T
, also called the isokinetic tem-

perature, must be higher than the glass transition temperature, T
. On the other hand,

it was shown that it was dicult to establish clear relations between the quantity
T
or its variations and the molecular structure of the polymers or the phenom-
enological characteristics of the glass transition (broadness, amplitude). Nevertheless,
it was suggested that the dierence T
was related to the breadth of the glass

transition.
For more on compensation phenomenon see Perez and Cavaille," Sauer and
Moura Ramos,"` Stepanov"` and Topic."" For deviation from the Arrhenius law that
can be described by a temperature-dependent (apparent) activation energy which
decreases with increasing T see Maass et al."`
3 Related dispersive processes
Dispersive kinetics, like dispersive transport and relaxation, is timescale invariant. In
the familiar continuous time random walk (CTRW) model, this feature is attributed to
the long-tailed distribution
+(t) :t? (58)
of time between events that limit the motion.
Hilfer and Anton"' have shown that there is a precise and rigorous relation between
the theory of continuous time random walks and the fractional master equation, i.e. a
master equation in which the time derivative is replaced with the derivative of
fractional order. The fractional master equation for a translationally invariant d-
dimensional system is written as
cS
ctS
p(r, t) _
P
w(r r')p(r, t) (59)
where p(r, t) denotes the probability density of nding the diusing entity at the
position r + R if it was at the origin r 0 at time t 0. The fractional transition rates
w(r) measure the propensity for a displacement r in units of [1/(time)]S, and obey the
relation _
r
w(r) 0. In integrated form
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p(r, t) o
r
"
1
I(o)
R
"
(t t')S _
r
w(r r')p(r', t')dt' (60)

where the initial condition p(r, 0) o
r
"
has been added. In the theory of CTRW the
basic equation of motion reads"`
p(r, t) o
r
"
u(t)
R
"
+(t t') _
r
z(r r')p(r', t')dt' (61)

for the case of no correlation between spatial and temporal behaviour. In eqn. (61), as
in eqn. (60), p(r, t) denotes the probability density of nding the diusing entity at the
position r + RB at time t if it started from the origin r 0 at time t 0. The probability
for a displacement r in each single step is denoted by z(r) and +(t) is the waiting time
distribution giving the probability density for the time interval t between two consecu-
tive steps. The condition _
r
z(r) 1 is obeyed.
It was shown"' that the fractional master eqn. (60) characterized by the kernel w(r)
and the order o corresponds to a special case of spacetime decoupled continuous-
time random walks characterized by z(r) and +(t). This correspondence is given by
+(u)
1
1 CuS
(62)
and
z(q) 1 Cw(q) (63)
where C is a constant, +(u) is the Laplace transform of +(t), z(q) and w(q) are given by
the Fourier transforms of z(r) and of the kernel w(r), respectively. Thus the above
correspondence denes the waiting time distribution uniquely up to a constant while
the structure function, z(q), is related to the Fourier transform of the transition rates.
Inversion of the Laplace transformation in eqn. (62) exhibits the form of +(t)
+(t; o, C)
tS
C
`
_
I"
1
I(oko)
t
S
C
I
(64)
The series in eqn. (64) was recognized as the generalized Mittag-Leer"` function,
denoted as E
SS
(x), and thus one has alternatively
+(t; o, C)
tS
C
E
SS
tS
C
(65)
The series representation (64) shows that the waiting time density is a natural general-
ization of an exponential waiting time density to which it reduces for o1
+(t; 1, C) (1/C)exp( t/C) (66)
For t ;0 one gets from eqn. (65)
+(t) :t>S (67)
and for t ;- and 0 o1
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+(t) :tS (68)
i.e. an algebraic tail considered previously, cf. eqn. (58). The fractional order o of the
time derivative in eqn. (59) is restricted to 0 oO1 as the result of the general
theory,"" and special signicance is attributed to the two limits o;1, cf. eqn. (66), and
o;0, for which +(t) ;1/t.
The spherical symmetric diusion equation of fractional order for the time, written
as
cB
U
R
P(r, t) A
c
cr
P(r, t)
d 1
2r
P(r, t)
(69)
was shown by Alemany"" to correspond, for integer spatial dimensions d 1 and
d 3, to the long-time description of the fractal time random walk, in which the
interjump density has the asymptotic form (t) :tA, with 0 2/d
U
1.
In this context, it is important to mention that Weron and Kotulski" have shown
rigorously that in the framework of the one-dimensional fractal time random-walk
model of relaxation the frequency domain response takes, in both nonbiased and
biased walk, the only possible ColeCole form. The underlying reason for this is the
specic form of the relaxation function determined in this model by the above
discussed Mittag-Leer distribution. See also Weron and Kotulski"` on the relation
of Mittag-Leer probability density and the Le vy-stable density as k ;0, and Gado-
mski"` for a fractional evolution equation of the order of 1/2 for the relaxation
function.
In kinetics the Mittag-Leer function appears in modelling of small ligand binding
to myoglobin at temperatures between 80 and 160 K."" Its use is rationalized by the
model developed by Berlin et al.,"` who have shown that the stretched exponential
exhibits practically the same temporal behaviour as the Mittag-Leer function within
a restricted time range.
Finally, we have to add that recently fractional calculus is encountering much
success in description of complex dynamics. In particular fractional calculus has
proved to be a valuable tool to handle the viscoelasticity, cf. Schiessel et al.,"' who
constructed fractional rheological equations on the basis of well known mechanical
models, especially the Maxwell, the KelvinVoigt, the Zener and the PoyntingThom-
son models. Many of these equations admit closed-form, analytical solutions in terms
of the Fox H-function of the Mittag-Leer type. Because of the restriction 0 oO1
in eqn. (59) one is limited to the stretched exponential. For a compendium of some
results from the theory of fractal function see Massopust;"` for discussion of Le vy
dusts, Mittag-Leer statistics, mass fractal lacunarity, and perceived dimension see
Blumenfeld and Mandelbrot."`
Bunde et al."" have reconsidered relaxation processes that exhibit a stretched
exponential behaviour. They have found that in those systems, where the relaxation
arises from two competing exponential processes, the size of the system may play a
dominant role. Above a cross-over time that depends logarithmically on the size of the
system, the relaxation changes from a stretched exponential to a simple exponential
decay, where the decay rate also depends logarithmically on the size of the system. This
result is thought to be relevant to large-scale Monte Carlo simulations, and should be
amenable to experimental verication in low-dimensional and mesoscopic systems.
104 A. Plonka
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For discussion of stretched exponential probability density function in terms of the
theory of extreme deviations see Frisch and Sornette."
Although less common than the stretched exponential, the exponential with a fractal
exponent greater than unity has been encountered in spectroscopy and in the study
of direct energy transfer in fractal systems with dynamic disorder,` see also below.
An apparently unrelated eld in which the modied exponential law has been used is
the study of life expectancy of humans in demography and health statistics, e.g. in the
study of survival functions of cancer patients. To this we should add the survival
statistics for microrganisms in a radiation eld, cf. Plonka and Bogus.` In these elds
both the stretched and compressed exponentials have been used.
A stochastic model for stretched or compressed exponential survival statistics has
been suggested by Vlad et al." based on the following assumptions. (1) The state of an
individual is characterized by a nite set of random variables z (z
, z
`
, . . .); the time
evolution of these variables is described by a non-Markovian stochastic process with
long memory. (2) In the state space of an individual there are some critical regions for
which the death of an individual can occur; for a state vector z belonging to a critical
region, there is a probability 0 p(z) O1 dierent from zero that the individual dies.
(3) Two characteristic fractal time laws are introduced, for the randombehaviour of an
individual at a given moment and for the long-range time correlations of the uctu-
ations in the state space of the individual, respectively. A systematic procedure for the
evaluation of the average survival function is suggested, based on a cumulant expan-
sion in terms of the bit number b ln[1 p(z)] of the probability of survival
corresponding to a state vector z belonging to a critical region. Explicit computations
are performed both for discrete and continuous time in the case of a non-Markovian
and Gaussian process with long memory describing the time evolution of the bit
number b. It is shown that the main cause for the occurrence of the stretched or
compressed exponential statistics is the fractal time behaviour for one-time uctu-
ations. The second-fractal time law, which describes the long-range correlations of
state uctuations, leads only to a correction which increases the value of the survival
function, i.e. the long memory uctuations of the state variables increase the chances of
survival of the individuals. Some implications of the model for the interpretation of the
survival data in population and health statistics were given.
By comparing their treatment of non-exponential survival functions with the univer-
sal physical model for non-exponential relaxation, Vlad et al." have noted that a
common feature of the models used in physics and biology is that the non-exponential
behaviour is due to the above mentioned occurrence of scale-invariant distributions of
fractal time processes. The main dierence is that while in physics one may assume that
the stretched exponential represents a kind of universal law, in biology the stretched or
compressed exponential survival functions are far frombeing universal. They generally
fail to represent the statistical data for the whole age range from birth to death. Their
use is mainly limited to the representation of survival data for terminally ill adult
patients, age being measured from the onset of illness. For instance, it is quoted that
the statistical data for breast cancer can be tted by a stretched exponential with
: 0.6, whereas the data for chronic myelogenous leukaemia correspond to a com-
pressed exponential with : 1.5. A closely connected topic is that of enhanced
diusion, discussed below.
Some unexpected analogies among a number of apparently unrelated problems
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were noted by Vlad et al.` They include the theory of rate processes with dynamical
disorder,'````'` the study of ergodic behaviour of stochastic cellular auto-
mata with long memory and of Mandelbrots fractional Brownian motion`" and
the study of enhanced diusion in disordered systems.`"
`` These analogies have

suggested that the doubly stochastic Poisson process`` is in fact a special type of rate
process with dynamical disorder which can be studied by applying the characteristic
functional techniques in the physical literature for the study of these processes."```
By combining this approach with a cumulant expansion technique developed for the
study of ergodic behaviour`" it is possible to investigate the eect of long-range
correlations of the uctuations of the counting rate on the statistics of the number N of
events occurring in a given time interval. It was stressed that until now this problem
has not been investigated in the physical, biological and statistical literature. For the
process of enhanced diusion in disordered systems we are interested in, it has been
shown that the long memory of the uctuations of the jump frequency leads to
enhanced diusion, provided that there is a preferred direction of the motion. For a
hopping mechanism of the displacement vector the theory predicts an anomalous
scaling exponent between one and two, where the maximum value (2) corresponds to
an innite memory and the minimum value (1) to an exponentially decaying short
memory. For a hopping mechanism in the velocity space the diusion exponent is
between 3 and 4, where the maximum value (4) corresponds to an innite memory and
the minimum value (3) (the Richardson exponent) corresponds to an exponentially
decaying short memory. These results are consistent with a complementary model for
enhanced diusion recently studied in the literature.`"` Despite the apparent
similarity of the predictions of the two models the corresponding physical mechanisms
assumed by the two approaches are however dierent. In ref. 120 and 121 the statistics
of the jump events is not given by a doubly stochastic Poisson process with a
uctuating jump rate but by a non-Markovian renewal process. For a general ap-
proach for describing the time evolution of a Markov process in continuous time and
with nite number of states see Vlad et al.`"
Relaxation
Kohlrauschs relaxation function remains a hot topic. According to Phillips`` the
ubiquitous character of Kohlrauschs relaxation function reassures us that we are
studying a universal phenomenon that transcends the details of material and probes
dierences in essentially all disordered solids. For the two magic stretching fractions,
[3/7 or 3/5, see Phillips`' and Phillips and Vandenberg.`` Even more encourag-
ing is the study of Jonscher`` on the universal relaxation law. The author nds it of
interest to dwell on the almost philosophical question of the reasons for the remark-
able universality of relaxational behaviour, which is observed in the following very
dierent contexts (asterisks denote the level of experimental information: *** very
strong, ** merits attention, * indications)
dielectric relaxation in dipolar materials***
dielectric relaxations in non-polar materials***
conduction in hopping electronic semiconductors***
conduction in ionic conductors***
trapping in semiconductors**
106 A. Plonka
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decay of delayed luminescence***
surface conduction on insulators**
chemical reaction kinetics***
mechanical relaxation**
magnetic relaxation*
For magnetic relaxation, the kinetic Ising models yielding the stretched exponential
behaviour for dierent choices of transition rate remain under study; cf. Brey and
Prados`" and Kisker et al.`" The eect of spin diusion on the decay of longitudinal
magnetization in deuterated glassy systems has been investigated by Hinze et al.`
Whereas in the supercooled liquid the longitudinal magnetization decays exponen-
tially in time, a crossover to a non-exponential decay is observed at a temperature
around the thermodynamic glass transition temperature. Below the glass transition
temperature the normalized magnetization curves are usually parametrized according
to a stretched exponential function. It is usually found that the average spinlattice
relaxation time increases with decreasing temperature, whereas the stretching par-
ameter [ rst decreases to a minimum value at a temperature somewhat below T
but
then increases monotonically as the temperature is lowered further. If experiments are
performed at dierent values of the Larmor frequency, a dependence of both the
average spinlattice relaxation time and [ on the Larmor frequency is observed.
Neither the temperature dependence nor the absolute values of stretching parameters
exhibit universal features, cf. Schnauss et al.`` Hinze et al.` report a strong correla-
tion between the apparent width of the distribution of spinlattice relaxation times,
inferred from numerical values of [, and the absolute value of the average spinlattice
relaxation time. This correlation is rationalized in terms of spin diusion.
Weiss et al.`` have determined the Kohlrausch exponent, [0.67 _0.03, for an
amorphous metallic system, Zr
'`
Al
``
Cu
```
, by anelastic relaxation measurements.
However, Durene et al.`" have found the Kohlrausch function to be inadequate to
model the shear and unaxial viscoelastic behaviour of soda-limesilica glass. Discuss-
ing the stress relaxation, Dobreva et al.`` have shown that Kohlrausch relaxation is
an approximation to dependencies following from the PrandtlEyring potential en-
ergy-barrier model of viscous ow of matter. The use of the stretched exponential
function to represent both the relaxation function
g(t)
G(t) G
`
G
"
G
`
(70)
and the retardation function
r(t)
J
`
t/p J(t)
J
`
J
"
(71)
of linear viscoelasticity for a given material was discussed by Berry and Plazek.`' In
eqn. (70) and (71) J(t) is the creep compliance, G(t) is the shear modulus, p is the
viscosity (p is nite for a uid and zero for a solid), G
`
is the equilibriummodulus G
for a solid, and zero for a uid, J

`
is 1/G
for a solid or the steady-state recoverable

compliance for a uid, G
"
1/J
"
is the instantaneous modulus, and t is the time. The
question was: if g(t) is given by exp[ (t/t)
@
], can r(t) be represented as exp[ (t/z)I]
for a linear viscoelastic uid or solid? It was concluded that g(t) and r(t) cannot both
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exactly be stretched-exponential functions for a given material. It was found, however,
that both g(t) and r(t) can be approximately represented by stretched-exponential
functions for the special case of a uid with exponents [ j in the range 0.5 to 0.6,
with the correspondence being very close for [j 0.5 and z 2t. Otherwise, the
functions g(t) and r(t) dier, with the deviation being marked for solids. For the
non-linear mechanical response of amorphous polymers below and through the glass
transition temperature region see also Gauthier et al.``
Jonschers`` own choice in respect of accepted theories lies with the stochastic
treatment of Weron et al. From among their recent developments one should mention
their reconsideration`` of two examples of physical phenomena, dielectric relaxations
and turbulent ows, where the Le vy-stable and extreme-value distributions appear
naturally. In the case of dielectric relaxations the common mathematical structure
underlying four dierent denitions of relaxation function, responsible for generating
the stretched exponential law, was found. In the case of turbulent ows, the distribu-
tion of velocities in a velocity eld produced by randomly distributed sources of
circulation was shown to be Le vy-stable with the characteristic exponent D/2, where D
denotes the fractal dimension of the turbulence. For a discussion on the universal
scaling of dielectric relaxation in dense media see also Dendzik et al.,`"
Thevanayagam,"" and Wagner and Richert." Rzoska et al."` have discussed
structural relaxation after switching o a strong electric eld in a near-critical solution
under high pressure.
A variety of microscopic mechanisms can give rise to stretched exponential relax-
ation, see e.g. Fujiwara and Yonezawa,"`
"` Huber,"'"` and Sciortino and Tar-

taglia."` New techniques of data analysis have been developed, cf. Macdonald.""`"
Sometimes, however, Kohlrauschs relaxation function is regarded as a convenient
phenomenological tool without fundamental signicance, cf. Go tze and Sjo gren.``
As stressed by Macdonald,` hundreds of papers are published each year which
make use of a distribution of relaxation times, or equivalently of a distribution of
activation energies, and many of them either directly involve a discrete or continuous
superposition of simple exponentials, cf. Section 2, equivalent in the frequency domain
to a superposition of simple one-relaxation-time Debye response functions, or can be
expressed in terms of such distributions of relaxation times. These treatments must be
rejected in principle if the results of Ngai et al.`` are indeed applicable. These authors
have argued that the PaleyWiener criterion, a necessary and sucient requirement
for the existence of a Fourier transform of a given function, predicted that a relaxation
function involving linear exponential decay was not acceptable. Macdonald` has
demonstrated that the PaleyWiener criterion does not, in fact, prohibit the existence
of a simple exponential relaxation function as a viable model for relaxation. For recent
attempts to obtain the distributions of relaxation times from frequency relaxation
spectra see Alvarez et al.,`` and for a determination of the distribution of relaxation
frequencies from experimental data see Dias.`"
The models for parallel relaxation can be classied in two dierent groups, cf. Vlad
et al.`` The random channel models (RCM) assume that there is a large number of
relaxation channels, any of them having a very small probability of being open.
According to this formulation,``'`` the average relaxation function of the pro-
cess can be expressed as
108 A. Plonka
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l(t),exp
"
j
H
(z)[1 zt]dz
(72)
where j
H
(z)dz is the average number of channels with an individual rate between z and
z dz. The general relationship (72) is thought to include the relaxation function
suggested in the literature. The random rate models (RRM) are based on the represen-
tation of the average relaxation function l(t), in the form
l(t),
`
"
P
5
(W)exp( Wt)dW (73)
where P
5
(W)dWis the overall probability of the total relaxation rate of the process.
Equations (72) and (73) can be used in two dierent ways. If the average number of
channels j
H
(z)dz or the probability P
5
(W)dW of the total relaxation rate can be
evaluated from theory, then eqn. (72) and (73) can be used for computing the average
relaxation function l(t),. If the average relaxation function l(t), is known from
experiment, then eqn. (72) or (73) can be used for evaluating the functions j
H
(z)dz or
P
5
(W)dW, respectively. Such an inverse approach has been commonly used in the case
of random rate models, for which eqn. (73) is an integral equation which can be solved
by means of a numerical inverse Laplace transformation. No similar procedures
seemed to be suggested in the case of random channel models.
Furthermore, in the literature there seemed to be a great deal of confusion concern-
ing the two formulations corresponding to eqn. (72) and (73). At rst sight it seems
strange that the same type of static disorder leads to two completely dierent expres-
sions for the average relaxation function l(t),. The dierent structures of eqn. (72) and
(73) may lead to the conclusion that they are incompatible with each other and then
they correspond to dierent models. The other extreme corresponds to the erroneous
idea that the statistical properties of the relaxation rates described by the functions
j
H
(z)dz and P
5
(W)dWshould be the same.
The general conclusion of the study of Vlad et al.`` is that the RCM and RRM
formulations of the theory of relaxation processes in systems with static disorder are
physically equivalent. The only dierence between them is of a formal nature; in the
case of the RCM formulation the static average of the survival function is expressed in
terms of the uctuations of the individual contributions of the dierent reaction
channels to the relaxation process, whereas in the case of the RRM formulation the
same average is expressed in terms of the uctuations of the total relaxation rate. These
results (see also Huber and Vlad``) pertain to systems for which the disorder is static.
Many important relaxation processes, however, occur in systems with dynamical
disorder; for these systems both the total and the individual relaxation rates, W(t) and
z(t), are random functions of time; cf. Huber,"' and Vlad et al.``" For these
processes knowledge of the average relaxation function is not enough for the complete
characterization of the rate statistics, not even in the case of the total rate approach. It
is thought that the lack of complete knowledge might be replaced by a maximum
information entropy estimate. For the maximum information entropy approach to
non-Markovian random jump processes with long memory see Vlad and Mackey.'"
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Transport
As recalled by Weeks et al.,' a wide range of diusive processes are interpreted as
random walks. A typical example is the Brownian motion of a passive particle in a
homogeneous uid, described as a sequence of steps generated by random collisions
with uid molecules. An ensemble of such particles spreads out with a variance
o`(t) 2Dt (74)
where D is the diusion coecient. For cooperative transport of Brownian particles
see Derenyi and Vicsek.'` Diusion of periodically forced Brownian particles moving
in a space-periodic potential has been discussed by Gang et al.'` The span of
Brownian motion in a eld in one dimension has been estimated by Makhnovskii et
al.'" Mathieu'` has studied the long-time asymptotics of a multi-dimensional
diusion with a random potential satisfying a scaling property; a subdiusivity prop-
erty has been proven. Heemink and Blokland'' reported on the non-trivial problems
encounteredin randomwalk models with space varying diusivity. The broad applica-
bility of the simple result, eqn. (74), is a consequence of the Central Limit Theorem: a
collection of sums of a large number of statistically independent events will be
Gaussian distributed, provided that the distribution of the individual event sizes is not
too broad. For more on Gaussian distributions see Puente et al.'` As applied to
random walks, the Central Limit Theorem implies that whenever the mean time
between steps and the mean square step size (the second moment of the step size
distribution) are nite, normal diusion will result.
In general, anomalous diusion
o`(t) :t
A
, "1 (75)
in physical systems is a consequence of correlations generated by spatial or temporal
coherence and the associated breakdown of the assumptions of the Central Limit
Theorem.
As an example, anomalous diusion in an aqueous system of a poly(ethylene
oxide)poly(propylene oxide)poly(ethylene oxide) triblock copolymer during gela-
tion was studied by Walderhaug and Nystro m'` by pulsed eld gradient NMR.
Ordinary diusion behaviour was observed in the sol phase. Anomalous diusion was
detected as the gel evolved. The mean square displacement o`(t) showed a power-law
dependence on time, eqn. (75), with 1. The value of decreased as the gelation
process proceeded, and was around 0.5 in the gel zone. It was recalled that in the
framework of fractal diusion Y2/d
`
, where d
`
2 is a random-walk fractal dimen-
sion. The slowing down of the diusion motionis caused by the delay of a diusing unit
because of a hierarchically intricate structure. In thermoreversible gelling polymer
systems, as in this case, it was expected that the formation of regions of enhanced and
reduced chain densities and reduced chain mobility due to physical crosslinks may give
rise to anomalous diusion. As a successful model for the description of gelation
processes, percolation theory in combination with the fractal concept, were consider-
ed. A gelling polymer system may be viewed as a percolating network that exhibits
self-similarity and can be described by a random fractal. A percolating network can be
characterized by the correlation length , which can be interpreted as a length scale up
to which the cluster can be regarded as fractal. Above the percolation threshold (an
innite cluster is present as well as nite clusters) the structure of the network may be
110 A. Plonka
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considered as homogeneous for length scales larger than and as fractal on length
scales L. In other words, represents the characteristic size of the voids in the
percolating system above the percolation threshold, and the characteristic size of a
nite cluster below the threshold (at this stage only nite clusters exist). In a percolat-
ing system, the systemlooks homogeneous on scales L and normal diusion holds,
while for a length scale less than , diusion is anomalous. The reason for this
anomalous diusion is the structure of the environment that alters the possible
diusion pathway by introducing extra tortuosity on a certain length scale. An
illustration of this eect is diusion in random percolating systems, known also as the
ant-in-the-labyrinth after de Gennes.'" By use of theoretical and simulation
methods for percolating systems, values of the anomalous exponent d
`
in the range
3.54.0 have been reported. Furthermore, experimental estimates`" of the anomalous
diusion exponent at the gelation threshold yielded a value of d
`
4.2. These results
suggest that the power law exponent 2/d
`
should be close to 0.5. It was noted that
there are also other theoretical models, based on a dierent conceptual background,
that predict a value of 0.5 of the power law exponent. The dynamics of short and long
polymer chains in melts and/or in concentrated solutions may be described in the
framework of the following models. For short chains, the dynamics in the Rouse limit
(hydrodynamic interactions are ignored) is governed by the Rouse time t
"
(the time for
a chain to diuse over the distance of its radius). For times much larger than t
"
, we
expect ordinary diusion to occur. At times t t
"
, only a portion of the length of the
chain has diused, and the mean square displacement of a polymer chain is predicted
to become proportional to t"`. For long chains, the dynamics of entangled polymer
molecules is frequently described in terms of the tube/reptation model. The reptation
of suciently long chains is characterized by a one-dimensional Rouse-like` cur-
vilinear diusive motion in an entangled tube formed by the topological constraints of
surrounding chains. This model is characterized by the so-called reptation or disen-
gagement time t
, since it is the time needed for the primitive chain to disengage from
the tube it was conned to at t 0, and the time t
, which denotes the onset of the

eect of tube constraints. The latter time is the time taken to diuse the interentangle-
ment distance, which is of the order of the mesh size of the network. For times t t
the dynamics is governed by the reptation process and ordinary diusion behaviour is
observed for the centre-of-mass motion. For t t
the chain behaves as a Rouse chain

in free space and anomalous diusion with a value of : 0.5 is predicted. The same
value of the power-law exponent is expected in the time interval t
"
t t
, for which
curvilinear diusion in the tube is probed. It is dicult to distinguish between the
above models, so it was thought of interest to discuss these results in light of the
ndings obtained from rheological measurements```` on the discussed system. At
long times, the stress relaxation modulus G(t) was found to exhibit a power law
behaviour of the form G(t) :tL, with n :0.5 at 37 and 40 C. This value of n is lower
than the percolation model prediction n :0.7. However, a dynamical scaling analysis
of exible fractals in the Rouse limit gives a viscoelastic exponent of n d
'
/(2 d
'
),
where d
'
is the mass fractal dimension. For example, the 0 chain with d
'
2 yields a
value of n 0.5. When it comes to the tube/reptation model, it is doubtful whether the
entanglement tube concept is relevant for the discussed polymer of a low molecular
weight (M:8000).
Knackstedt et al.`" performed water self-diusion measurements in ternary micro-
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emulsions (didodecyldimethylammonium bromide, water and cyclohexane) near the
structural transition point. Time-dependent diusion was observed and the scaling
behaviour was seen to be consistent with scaling characteristics expected for perco-
lative media. For the role of percolation in diusion on randomlattices see e.g. Ho rner
et al.;`` for survival probability for diusion on a percolation cluster see Palacz et
al.;`' for percolation transition into random Sierpinski carpets see Perreau et al.;``
for renormalization group approach to the bound percolation on Sierpinski carpets
see Lin et al.;`` and for series expansions for the ideal chain problem in Sierpinski
carpets see Aarao Reis and Riera.`"
Single-le diusion refers to motion in one dimension where the diusing molecules
are unable to pass each other. Such motion is dierent from unidirectional diusion, in
which the molecules move in one dimension but can pass each other. An important
distinguishing feature of single-le motion is that the mean square displacement of the
molecules scales as the square root of the observation time, i.e. 0.5. Experimental
evidence for single-le motion, a phenomenon that is probably widely prevalent in
both industrial catalytic and biological systems, was provided by Gupta et al.`" from
their pulsed eld gradient NMR studies of ethane diusion in large crystals of the
molecular sieve AlPO
"
. NMR evidence of anomalous molecular diusion (subdiu-
sion) due to structural connement was presented by Appel et al.` for polydimethyl-
siloxane in the porous matrix of polypropylene.
Settles and Doster`` reported a neutron scattering study of hydrated myoglobin.
Anomalous diusion of adsorbed water was evidenced. For anomalous diusion
displayed by molecular dynamics simulations at the proteinwater interface see Bi-
zzarri et al.`` The dominance of interaction-based constraints to diusion is sugges-
ted by Sidebottom et al.`" in their anomalous diusion model of ionic transport in
oxide glasses. For examples of diusion treatment under structural connement see
the reports of Revathi and Balakrishnan```' and Aslangul`` on diusion coe-
cients fromrandom-walk modelling on strips. The concept of fractal dimensions seems
to be a fruitful starting point for numerous studies of diusion under structural
connement, cf. the reports on diusion on a random comb by Aslangul et al.,``
Balakrishnan and van den Broeck`" and Revathi et al.,"" on a dumb-bells random
walk in continuous time by Alemany et al.," and on a continuous-time random walk
of a rigid triangle by Sokolov et al."` See also Balakrishnan"` for a random walk on
random fractals, Sartoni and Stella"" for a nite-size analysis of biased diusion on
fractals, and Barta and Dieska"` for a study of anomalous diusion on percolating
clusters near to the critical point.
Weeks et al.' have studied the anomalous diusion arising from random walks
with discrete steps of constant velocity separated by pauses (sticks) of random dur-
ation. Asymmetric random walks of this form were used to model the rst experimen-
tal observations of anomalous diusion of electrons in amorphous materials"'"`
and were studied theoretically for cases with broad distributions of sticking times but
with narrow distributions for ight length."` Weeks et al.' considered power law
forms for both sticking and ight distribution functions and provided the rst compre-
hensive analysis of the relationship between and the sticking and ight distribution
exponents for both symmetric and asymmetric random walks. Random walks with a
broad sticking and ight distributions can be found in Hamiltonian systems, cf. Weeks
et al.' In a map representation, maps with power-law sticking behaviour and ight
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behaviour appear to be common; see also e.g. Tasaki and Gaspard,""`"" Bettin et
al.`" or Ishizaki and Mori.`"`
For simple cases, as given by eqn. (74), the variance of an ensemble of random
walkers grows linearly with time, the diusion constant D being given by
D
l`,l,`
2T
(76)
The moments of l are based on P
'
(l), the distribution of step sizes (or ight sizes), and T
is the mean time between the starts of successive ights. This result depends only on the
rst two moments of the step size probability distribution function and nite non-zero
T, and not on other details of the random walk. The mean position of random walkers
is
x,
l,
T
t (77)
which is zero for a symmetric (l, 0) random walk.
For probability distribution functions that decay suciently slowly, the Central
Limit Theorem no longer applies. If P
'
( l ) : l I and j3, the second moment
l`, is innite (j1 for the distribution to be normalizable). A random walk for this
type of probability distribution function is a Le vy ight, and the variance scales with
time according to eqn. (75) with
2, 1 j2 (78)
4 j, 2 j 3 (79)
1, j3 (80)
In addition, for j 2 the variance grows as t`/lnt, and for j 3 the variance grows as
tlnt. These results are valid when the random walker moves at constant velocity,
taking ights with a length distribution given by P
'
( l ), or equivalently, a distribution
of ight times having the same asymptotic power law behaviour. In addition, the time
T must be nite. Superdiusive transport, 1 2, occurs for 2 j 3. When
2, the transport is ballistic, i.e. the exponent is the same as that of a collection of
particles moving in dierent directions in straight lines, with no pauses or changes in
direction.
To consider cases where T;-, Weeks et al.' have allowed the random walker to
pause (stick) between steps, and introduced the sticking time distribution (also called
trapping distribution). Again, they assumed the behaviour at long times decays as a
power law: P
`
:tJ. When v 2 (with v 1 for normalization), t
'
, (the rst moment
of the sticking probability distribution function) is innite and the variance has the
possibility of scaling subdiusively. Shlesinger"` investigated the case where random
walkers were stuck for varying times between random (symmetrically chosen) steps
with nite mean square step (j3), nding
1, v 2 (81)
v 1, 1 v 2 (82)
Shlesinger"` also considered random walks with asymmetric steps (l,"0) and
found the scaling of the mean, x,:l,t@ with
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[1, v 2 (83)
[v 1, 1 v 2 (84)
and the scaling of the variance, o` :tA, with
c 4 v, 2 v 3 (85)
2v 2, 1 v 2 (86)
According to Weeks et al.' for a broad distributionof ight times (j3), the motion
is superdiusive (1 2), and the probability distribution function has a divergent
second moment, i.e. it is a Le vy distribution. For a broad distribution of sticking times
(v 3), either superdiusion or subdiusion ( 1) can occur, with qualitative dif-
ferences between symmetric and asymmetric walks. For narrow probability distribu-
tion function (j3, v 3), normal diusion ( 1) is recovered. Predictions of the
model were related to experimental observations of transport in a rotating annulus; see
also Klafter et al.`"` For anomalous diusion and probability distributions see also
Porra et al.,`"" who studied the motion of a particle governed by a generalized
Langevin equation. Balescu et al.`"` have analysed in great detail a test problem, the
exact solution of which can be obtained analytically, in order to establish the relation
between the Brownian motion or Langevin approach and the kinetic theory approach
to anomalous transport. The conclusion of the analysis is that the equivalence of the
two approaches is by no means automatically guaranteed. The status of the stochastic
theory of reaction-diusion systems based on master equation was investigated by
Baras and Mansour`"' by microscopic simulations. The result is that the theory can
only be guaranteed over length scales not smaller than the reactive free path. For
thermodynamics of anomalous diusion see Zanette and Alemany,`"` who generaliz-
ed the Einstein relation of diusivity and temperature for random walks of Le vy-ight
type. Andreozzi et al.`"` presented evidence of a fractional law
D:(p/T)D, 0 O1 (87)
for the rotational dynamics of nearly spherical and cylindrical tracers in supercooled
o-terphenyl. Binder`"" has shown that fractal Brownian motion with long-range
correlations can be obtained by performing a power-lawcoordinate transformation of
the ordinary diusion equation in time or in space. Enhanced diusion upon ap-
proaching the kinetic glass transition was discussed by Liu and Oppenheim.`"
Many recent studies of electron transport in molecularly doped polymers`
`" in
vapour deposited molecular glasses``
`` and layers`` as well as hole transport in

molecularly doped polymers`"
``` and in vapour deposited molecular glasses``'
``"
were analysed in terms of the formalism due to Ba ssler.``" In this formalism it is
assumed that charge transport occurs by hopping through a manifold of localized
states with superimposedenergetic and positional disorder. The principal assumptions
are as follows: (1) the distributions of hopping site energies and distances are Gaus-
sians; (2) the jump rate can be described by an expression originally proposed by Miller
and Abrahams`` to describe low temperature impurity hopping in semiconductors
v
GH
v
"
exp( 2r
GH
)exp
c
H
c
G
eEx
kT
, c
H
Pc
G
v
"
exp( 2r
GH
), c
H
Oc
G
(88)
where c
G
and c
H
are site energies, e and E are the electric charge and eld, and is the
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coupling parameter; (3) electronphonon coupling is suciently weak that polaron
eects can be neglected, yet strong enough to guarantee coupling to a heat bath; and (4)
the process is incoherent, characterized by a loss of phase memory after each jump.
The key parameter of the formalism, displayed by simulations,``` is the width of the
hopping site energies, or DOS (density of states), o, which largely determines the
temperature dependence of the mobility. Zero-eld mobility at temperature T is given
by
j(T) j
"
exp
2o
3kT
`
(89)
where j
"
represents what the mobility would be if there were no energetic disorder, i.e.
if o were 0. The eect of permanent dipoles on the function of an array of hopping sites
was examined by Dieckmann et al.,``` by summing the contributions of individual
dipoles to the total potential at a given site. For relative dipolar site concentrations
0.1, the DOS function is of Gaussian shape. At lower concentrations, it approaches
a Lorentzian. Good agreement with literature data on the dipolar contribution to the
DOS function for hole transport in molecularly doped polymers and molecular
glasses, diering with regard to dipole moment and concentration of dipolar moieties,
was found.
The distribution of nearest neighbours in dilute hopping systems was shown by
Arkhipov and Ba ssler``" to be determined completely by positional disorder. As a
result, there is no interplay between the energy and distance as far as the easiest jump is
concerned, and the distribution in energy of hopping neighbours parallels the density-
of-state distribution function. As a result the dependence of the charge carrier mobility
on concentration and temperature can be factorized into terms dependent on concen-
tration and temperature only. These dependencies were calculated for the case of a
completely random spatial distribution of localized states. The temperature depend-
ence of the transport coecients in dilute systems was shown to coincide with that in
systems with a high concentration of hopping sites.
According to the analysis of Young and Fitzgerald,``` in most cases analysed much
of the variation in the mobility is a consequence of variations in the degree of energetic
disorder, which tends to increase with increasing dipole moment. Nevertheless the
prefactor mobility also varies considerably and rather nonsystematically. There is
reason to suspect that the group dipole moments of the individual donor moieties are
at least as important as the net moment in determining the degree of energetic disorder,
so that it becomes hard to connect trends in energetic disorder with the observed
correlation of the room-temperature mobility with net dipole moment. Furthermore,
the intramolecular disorder and presence of two or more chemically distinct species in
some molecules are likely to lead to non-Gaussian distributions of site energy.
Young``' analysed the eects of geometrical disorder on hole transport in molecularly
doped polymers, nding some advantages for the use of the recent modication of the
model.``` For eects of polar additives on charge transport in a molecularly doped
polymer, see also Young and Fitzgerald.```
`" For a low-temperature approximation

to Ba sslers random-walk model see Dyre.`"` Argyrakis et al.`"` have studied the
hopping transport of particles in the presence of randomly distributed energy barriers
for diusion. Exponential, Gaussian and uniform distributions of barrier heights on
square and simple-cubic lattices were investigated to uncover the inuence of the form
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and width of the distributions. The temperature dependence of the characteristic time
separating the initial regime of anomalous diusion from the long-time normal diu-
sion is of an Arrhenius form, with an eective activation energy determined by the
percolation threshold of the corresponding lattice. Their analytic results, derived
within the framework of the eective medium approximation, show that the asym-
ptotic diusion coecient does not depend on the degree of disorder on a square
lattice, whereas on a cubic lattice it does. These predictions are conrmed by numerical
simulations. The temperature dependence of the diusion coecient is also deter-
mined by the coordination number z of the lattice for static barrier disorder. On a
square lattice it is of an Arrhenius form, and for z "4 it deviates therefrom with
increasing degree of disorder. It is always non-Arrhenian in the case of dynamically
changing disorder.
The mean number of distinct sites visited by N non-interacting n-step Le vy ights
was studied by Berkolaiko et al.`"" in one dimension and Berkolaiko and Havlin`"` in
d dimensions. The distribution of the number of distinct sites visited by random walks
in disordered lattices has been discussed by Gallos et al.,`"' Webster`"` has given the
exact probability distribution governing the length of a random walk of equal steps.
Molinas-Mata et al.`"` have introduced and investigated a random-walk model in
which the walker is scattered only when a site is visited by the walker for the rst time.
Subsequent visits to these sites have no eect on the walker. As a result, the walker
follows straight (ballistic) trajectories between random changes in its direction. Exten-
sive numerical simulations on a two-dimensional square lattice have been carried out
to show that the motion is subdiusion. A mean-eld theory was developed that
accounts for the subdiusive behaviour and for the asymptotic density of unvisited
sites.
Le vy ights constitute an interesting generalization of ordinary Brownian walks.
Here the step size is drawn from a Le vy distribution which has a long-range algebraic
tail corresponding to large but infrequent steps, so-called rare events. The built in
superdiusive characteristics of Le vy ights have been used to model a variety of
physical processes. Fogedby`"" has considered Le vy ights in the presence of a
quenched random force eld and has examined the interplay between the built-in
superdiusive behaviour of Le vy ights and the pinning eect of the random environ-
ment, generally leading to subdiusive behaviour. Habasaki et al.``" have examined
the relaxation behaviour of alkali metal ions in lithium metasilicate glasses by means
of a molecular dynamics simulation. They have observed a change of the slope of the
mean-squared displacement at ca. 300 ps. In shorter time regions, localized motion of
lithium ions within neighbouring sites was observed, which is caused by the small
fracton dimension (fracton excitation). On the other hand, an accelerated motion of
particles due to cooperative jumps was found, which characterizes the diusion and
conduction mechanisms of the alkali metal ions at longer times. The dynamics of
accelerated motion was discussed in relation to Le vy ight dynamics.
Le vy diusion and classes of universal parametric correlations have been discussed
by Kusnezov and Lewenkopf.`` Fractal generalization of Brownian motion has
proved to be a rich eld in probability theory, statistical physics and chaotic dynami-
cs.``` The movement of charged particles gives rise to frequency-dependent conductiv-
ities which can be studied experimentally. Most investigations are, however, restricted
to the determination of the so-called d.c. conductivity which results from successful
116 A. Plonka
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hops of the mobile species. Being caused by successful hops, the d.c. conductivity
describes the long-time dynamics only. As an example, recent studies of Pimenov et
al.``` on structural relaxation in a molten salt, probed by time-dependent d.c. conduc-
tivity measurements, covered the time range 60106 s. On the other hand, the fre-
quency dependent conductivity, o(o), is determined by the dynamics occurring in a
time window which is the inverse of the angular frequency o. Cramer``" has analysed
the conductivity spectra, o(o), covering wide frequency ranges up to the mid-infrared.
The systems discussed include the ion-conducting glasses 0.30Na
`
O0.70B
`
O
`
,
0.30Li
`
O0.70B
`
O
`
and B
`
O
`
0.56Li
`
O0.45LiBr as well as the polaron-conducting
glass 0.2P
`
O
`
0.8(0.89V
`
O
`
0.11V
`
O
"
). In the case of ion-conducting glasses it was
possible to separate vibrational (high-frequency) and hopping (low-frequency) spectra
fromeach other. The resulting hopping spectra display high-frequency plateaux; in the
dispersive regime, two power-lawexponents are observed, one being smaller, the other
larger than unity. In contrast, the dispersive conductivity of the polaron-conducting
glass shows a simple single-power-law behaviour with an exponent smaller than one,
i.e. it follows the power-law behaviour introduced by Jonscher```
o(o) :o(0)[1(ot
`
)N], 0 p 1 (90)
where o(0) denotes the d.c. conductivity and 1/t
`
marks the onset of the power-law
dispersion on the angular frequency scale. Whereas the overall dynamic conductivity
of the polaron glass turned out to be successfully described by the jump relaxation
model, cf. Funke,``' a model termed unied site relaxation model was used to
rationalize the data for ion-conducting glasses; see also Cramer et al.,``` Funke``` and
Funke and Cramer.``"
In the time domain, the use of a Kohlrausch function to describe conductivity
relaxation is rationalized, cf. Reau et al.,`'"`' by the coupling model. According to
Ngai and Martin`'` the departure from linear relaxation results from cooperation
between charge carriers in conductivity relaxation: the jump of a mobile ion in a glass
may not be treated as an isolated event: it causes a time-dependent motion of other
charge carriers in the surroundings, which leads to additional relaxation of the applied
eld. It results in a value of the [ parameter that becomes smaller as the cooperation
between charge carriers is more extended. In this model there is no place for a
distribution of relaxation times and therefore of activation energies. Quite an opposite
example is provided by Kim et al.`'` They have reported `Li nuclear spin-lattice
relaxation measured at 4, 12.1 and 22 MHz, and conductivity measured from 1 Hz to
10 MHz, from 100 to 500 K, on a series of xLi
`
S(1 x)GeS
`
glasses with x0.35,
0.45 and 0.55. These data were used to examine the quality of the model for the ionic
motion and the ionic conductivity in Li> glassy fast ion conductors obtained by
describing the ionic hopping motion with a distribution of activation energies derived
from the `Li nuclear spinlattice relaxation. They have found that the distribution of
activation energies obtained from nuclear magnetic relaxation and the percolation
threshold in the barrier distribution obtained from conductivity match.
Non-exponential relaxational eects, typically known for disordered materials, were
found by Kno dler et al.`'" for a Coulomb lattice gas containing randomly placed
immobile counterions. An analytical, microscopic treatment which can be used to
describe the relaxation processes of hopping ionic conduction from the adiabatic
region to the isothermal region with equal rigor has been developed by Sato et al.`'`
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for lattice gas systems. It was found that the relaxation motion of a single particle in the
assembly is intrinsically non-Debye and follows the Kohlrausch relaxation behaviour
even without interactions among ions. This is an apparent contrast to the current view
that the anomaly is created by interaction and disorder.
Hartenstein et al.`'' have presented the comparison between multiple trapping and
multiple hopping transport in a randommedium. It was recalled that the rst explana-
tion of dispersive transport was provided by Scher and Montroll,"' who applied the
CTRWtheory to experimental observations. In this theory transport of charge carriers
in a random medium under the inuence of an electric eld is described phenom-
enologically in terms of generalized waiting-time distribution. Disorder gives rise to
broad waiting time distribution. By introducing a waiting-time distribution of the form
of expression (58) in a heuristic manner, Scher and Montroll were able to showthat the
associated current must feature a time dependence of the form
I(t) :
t>?
t?
t Ot
O
t t
O
(91)
where, as before, : is the dispersion parameter and t
O
the eective transit time, which is
dened as the break in the slope of a plot of ln I(t) vs. lnt. Waiting-time distribution
function and transient current are thus predicted to be dispersive and controlled by the
same dispersion parameter.
The CTRW formalism for an exponential density of states leads to the same time
behaviour as the multiple trapping model,`'` the physical picture being that the
motion of independent charge carriers at the edge of the conduction (or valence) band
is interrupted by temporary trapping events by localized states. The multiple hopping
model remains under discussion. As far as the current transients are concerned the
equivalence of the models had been demonstrated for an exponential density of
states.`'` Hartenstein et al.`'' have studied the motion of excess charge carriers in a
random medium via either multiple trapping or multiple hopping, both analytically
and via simulation for an exponential as well as Gaussian density of states. Waiting
time distribution as well as transient current calculated under the premise of multiple
trapping transport agree with the equivalent quantities obtained for the multiple
hopping case via simulation. This indicates that at low elds the experimental signa-
tures of both transport mechanisms are indistinguishable, despite dierences concern-
ing the underlying elementary processes. The waiting time distribution for a Gaussian
density of states deviates from an algebraic law.
A critical comparison between geometrical networks (based on some bonding
criterion) and kinetic networks (the actual path of the carrier) has been done by Brown
and Esser`'" for dispersive hopping in disordered systems. The method of order
statistics was used for the characterization of the kinetic network. These statistics
describe the distributions of rst, second and higher transition rates out of a given site
to other sites in a hopping conguration and can adequately explain the structure of
the kinetic network for the strong disorder case, via consideration of chain growth vs.
branching. Using numerical simulation a detailed investigation of howthe structure of
the kinetic network changes with increasing disorder is presented. When disorder is
strong, the kinetic network becomes predominantly one-dimensional and is actually a
small subset of the geometrical network. As one of the consequences, the kinetics due
to capture at recombination centres slows down and becomes close to behaviour
118 A. Plonka
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typical for one dimension. An analytical study, veried by Monte Carlo simulations,
for one-dimensional disordered systems has been presented by Siebbeles and Be-
rlin.``" See also Berlin and Burin`` and Berlin et al.```
Trap-controlled dispersive transport and recombination were considered by Ar-
khipov and Adriaenssens``` for materials with uctuating localized states. Under
these conditions the distribution of eective activation energies can be dierent from
the momentary energy distribution of localized states. The former rather than the
latter governs kinetics of all processes which are controlled by trapping and release of
charge carriers. It is shown that distribution of eective activation energies and the
momentary distribution are rather similar for shallow states and can be very dierent
for suciently deep traps. As a result, the uctuations do not aect dispersive trans-
port characteristics at short times, but either terminate the dispersive transport or
make its characteristic temperature independent at longer times. See also Arkhipov
and Adriaenssens.``" For statistics of transport in disordered conductors see Lee et
al.,``` and for analysis of the energy landscape for charge transport in polar glassy
materials see Richert and Loring.``'
Chaotic dynamics
The once abstract notions of fractal space and time now appear naturally and
inevitable in chaotic dynamical systems and lead to strange kinetics and anomalous
transport properties. An understanding of this kind of dynamical behaviour should
provide insight into particle random-walk processes.``` Indeed, the theory of dynami-
cal chaos has changed our view of the possibility of nding a foundation for statistical
laws, since the dynamical trajectories, which are the solutions of the deterministic
equations of motion, may resemble the curves representing random processes.``` As
quoted in Ref. 278, analysing the foundations of quantum mechanics, Einstein made a
well known remark, God doesnt play dice with the world. Now one may add to those
words that, from the standpoint of classical physics only, God does not have to play
dice, since dynamical equations can themselves give rise to stochastic processes if
certain simple restrictions to the parameters and initial conditions are applied.
To introduce the subject we will follow Zaslavsky``` (see also Zaslavsky et al.``"),
and recall that according to the Poincare Recurrence Theorem a trajectory of a
Hamiltonian system, having started from some small area A, returns to this area an
innite number of times. Let T
H
be a time interval between the (j 1)th and jth return,
then the variable T
H
is an element of an innite sequence:
T YT
, T
`
, . . . , (92)
and is referred to as a recurrence time.
No information at all about the nature of the T sequence follows from the
Poincare Recurrence Theorem. Under conditions of dynamical chaos the sequence
T is random, and it is possible to raise the questionof the probability distribution for
the recurrence time, f (T), which has to be normalized
`
"
f (T)dT1 (93)
Under normal conditions
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f (T) (1/T,)exp( T/T,) (94)
where T, is an average recurrence time,``" and for the simplest cases
T,1/h (95)
where h is the KolmogorovSinai entropy, cf. Sinai.``
The results (94) and (95) are rationalized in the following way. For systems with
dynamical chaos, the number of periodical orbits with period less than T is asymptoti-
cally equal to``
N(T) :exp hT (T;-) (96)
If the recurrence time is very large, a cycle of the unstable periodical curve diers only
slightly from the random non-periodic curve that returns to a small area A. This is
justied by the Poincare cycle for the return to the small area A. An open cycle can be
turned into a closed one by an exponentially small stirring of the initial condition.
Formula (96) demonstrates that there are an innite number of ways for closing the
trajectory. Therefore N( T) is proportional to the envelope phase volume for the
periodical orbits with a period OT. Hence the probability density of appearance of an
orbit with a given period T is
P(T) :const/N(T) (97)
and this should have the same magnitude as the probability density of the recurrence
f (T). Substituting eqn. (97) into eqn. (93) one gets eqn. (94) and (95). In fact, the
distribution of the recurrence times has a more complex structure because real systems
with dynamical chaos are not equivalent to, for instance, a system of the Sinai billiard
type.`` The phase space of a dynamical system is strongly non-uniform. Within areas
with chaotic dynamics there are islands which are not penetrated by the trajectories
from the chaotic area. The borders of the islands are sticky, i.e. having entered a very
narrow band at the border, the trajectory remains trapped there for a long time. This
property of trajectories crucially inuences the large timescale asymptotics.
To understand the possible consequences of stickiness we have to consider``` a
small area of the phase space A with volume I
. Within A there is always an area A
with volume I
consisting of particles that leave A within a limited time period t
,
since otherwise it would not have been necessary to prove the return of the particles.
Similar reasoning can be used in considering the exit of particles from the area A
`
,
which should occur within a certain time period t
`
. Hence the particles assume a new
position, i.e. the area A
`
with volume I
`
I
"0 and A
A
`
0, since otherwise
the particles accumulate in A
. If the particles performing a nite motion never return

to the initial area A, then I
I
`
. . . - because all I
are equal, which

contradicts the condition of niteness of motion. Hence the particle must return to Ain
a nite time T. The above reasoning demonstrates that a return time cannot be less
than an exit time from the area A, which can be measured relatively easily. Let +(t)dt
be the probability that a particle exits the area A in a time t which falls within the
interval (t, t dt). Then the probability of the particle leaving the area A in the time
Ot is
u
(t)
R
"
+(t)dt, u
(-) 1 (98)
120 A. Plonka
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(escape probability); and the survival probability is
u
'
(t)
`
R
+(t)dt 1
R
"
+(t)dt 1u
(t)
(99)
u
'
(-) 0
Under normal conditions the magnitude +(t) :f (t), and consequently it decreases
exponentially with time. However, the stickiness phenomenon can lead to a totally
dierent pattern of returns or escapes. Numerous simulations, as well as the analysis of
some simple models (cf. e.g. Zaslavsky and Tippett,``" Meiss and Ott,``` Meiss,`````"
Ding et al.,``` Zaslavsky et al.,``' Benkadda et al.,``` Afraimovich and Zaslavsky```
and Zaslavsky and Niyazov``"), point to the existence of asymptotics
+(t) :t@, [ 0, t ;- (100)
in real models of Hamiltonian chaos (see also Meiss`""). In this case formulae (98) and
(99) result in the following possibilities for the survival time t
'
t
'
Y
`
"
t+
'
(t)dt :
"''
"
t+
'
(t)dt
`
"''
tdt
t@>
const, [1
ln
R
`
t, [1
-, [1
(101)
In the case [ O1 the average survival time t
'
is innite. According to Zaslavsky``` this
result seems never to have been seriously discussed in terms of the Poincare Recur-
rence Theorem. To avoid a seeming discrepancy one should understand the dierence
between individual events themselves and the frequencies of their occurrence (i.e. the
probabilities). Although a particle always returns to the initial area within a nite
period of time (the Poincare Theorem), the frequencies of recurrence times can be such
that an average recurrence time t
'
will be innite (t
'
t
'
-).
As stressed by Shlesinger et al.``` the real orbits of dynamic systems are always
theoretically predictable because they represent solutions of a simple system of equa-
tions (for example Newtons equations). Under conditions for dynamical chaos, how-
ever, these orbits are highly unstable. Generally for chaotic motion the distance
between two initially close orbits grows exponentially with time as
d(t) d(0)exp(zt) (102)
where the rate z is called the Lyapunov exponent.`" This dependence holds for
suciently long times. Local instabilities, described by eqn. (102), lead to rapid mixing
of orbits within the time interval t
H
1/z. Nevertheless, some properties of the system
remain fairly stable, and their evolution occurs at a signicantly longer timescale,
t
'
t
H
, as a result of averaging (possibly only partially) over the fast process of mixing,
caused by the instability in eqn. (102). Kinetic equations arise as a consequence of such
averaging. The well known Gaussian and Poissonian statistics (for diusion in space
and temporal measures, respectively) can under certain conditions give a valid, albeit
approximate, description of the apparent randomness of chaotic orbits. It has been
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realized, however, that types of behaviour much more complex than standard diusion
can occur in dynamical Hamiltonian chaos. For Hamiltonian chaos Shlesinger et
al.``` have emphasized a parameter regime where Le vy statistics (describing fractal
processes ) apply and a strange kinetics rules. Le vy statistics can appear both in space
and time, and the fractal processes they describe lie at the heart of complex processes
such as turbulent diusion, chaotic phase diusion in Josephson junctions,`"` and
slow relaxation in glassy materials. To that we would like to add dispersive chemical
kinetics.`"`
It is recalled`"" that in the modern theory of dynamical systems, chaos is character-
ized in terms of quantities such as the Lyapunov exponents, the KolmogorovSinai
entropy and the PollicottRuelle resonances.`"` In the context of non-equilibrium
statistical mechanics, these quantities are dened at the microscopic level of descrip-
tion, in contrast to the transport and reaction rate coecients that characterize the
macroscopic level. If a direct connection could be established between quantities at
both levels, the non-equilibrium stationary states could then be dened at the micro-
scopic level in terms of the invariant or conditionally invariant, real positive or
complex measures on which the characteristic quantities of chaos are dened. In this
way, the rigorous non-equilibrium statistical ensembles could be identied at the level
of the microscopic dynamics, and a fundamental understanding of irreversible pro-
cesses would be reached.
At a macroscopic level one item of interest is the asymptotic scaling laws, written as
R(t) , :tI (103)
where R(t) is the displacement of a particle and the averaging is over all particles. The
case j 0.5 is considered as normal transport in view of its resemblance to Brownian
motion [cf. eqn. (74)]. For 0 j0.5 captured particles dominate. For 0.5 j 1,
so-called Le vy ights prevail, and the transport is referred to as anomalous. Since eqn.
(103) describes a property that holds for large t and R(t), it gives a large-scale property
of the system. In contrast, the parameter j has to come from the microscopic or local
properties of the phase space. The microscopic behaviour is described in a geometric
way (fractal dimensions), which is in some sense physically unobservable, whereas the
microscopic diusion is a fairly explicit process. One would like to be able to observe
macroscopic properties from the local measurements of the system. The measurement
of Poincare recurrence times is believed to do just this.``"
As recalled by Dorfman et al.,`"' a study of the relation between transport coe-
cients and chaotic behaviour for purely Hamiltonian systems has been initiated by
Gaspard and Nicolis.`"` The transport coecients for uid systems are related to the
escape rate of a set of trajectories from a certain well dened region in the appropriate
phase space. Typical of the results of this approach is the expression for the coecient
of diusions D of a single moving particle in an unbounded region with a xed array of
scatterers
D lim
*
_
H
G
"
z
G
(F
*
) h
'`
(F
*
)
(104)
Here one considers all trajectories of the moving particles such that their x-coordinate
remains within the interval
L/2 Ox OL/2 (105)
122 A. Plonka
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Most trajectories, except for a set of measure zero, will eventually leave the interval.
However, there is a fractal set of trajectories F
*
that never leave the interval. Then
z
G
(F
*
) is a Lyapunov exponent for trajectories on the fractal set, h
'`
(F
*
) is the Kol-
mogorovSinai entropy per unit time for trajectories on the fractal set, and only the
positive (separating) Lyapunov exponents are summed over in eqn. (104). A direct
relation exists between quantities of interest for the description of irreversible pro-
cesses in uids and quantities such as the Lyapunov exponents and Kol-
mogorovSinai entropies that describe the fundamental dynamical behaviour of the
phase-space trajectories of the same system.
Dorfman et al.`"' described the methods by which dynamical systems theory can be
applied to Lorentz lattice gases with stochastic collision rules governing the interac-
tions between a moving particle on the lattice and xed scatterers distributed on lattice
sites. This system is simple enough that the applications of dynamical systems theory
to it can be made very clear, and all transport and dynamical properties of interest can
be calculated in full detail. These properties include the diusion coecient, Lyapunov
exponents, KolmogorovSinai entropies, and a number of related quantities. The
paper`"' is intended to introduce some of the essential ideas of this approach to
non-equilibriumprocesses for a simple example. It draws upon elementary mathemat-
ical arguments and models to show that the Lorentz lattice gas can be thought of as a
dynamical system with many of the properties normally present in chaotic Hamil-
tonian systems. A full description of this line of research on Lorentz gases is pres-
ented.`"` It is shown that the Lorentz lattice gas belongs to the category of systems
such that their transport properties can be characterized by the dynamics of a fractal
set of trapped trajectories. Dorfman et al.`"' have computed these chaotic properties
of open systems using both analytical and computational methods, in order to illus-
trate eqn. (104) for Lorentz lattice gases and to develop further consequences of the
approach to transport phenomena. For more details see Ernst et al.,`"` Yukalov and
Yukalova`"" and Beijeren et al.`""
The changes of the spectrum of Lyapunov exponents for a metalinsulator transi-
tion are given by Markos and Henneke`" and Markos.`"` Zhao`"` reports a study of
dynamical intramolecular energy transfer in a realistic polyatomic molecular model
system of cyclobutanone. For this model with two degrees of freedom, Lyapunov
relaxation does yield the same timescale as intramolecular energy exchange. The
development of nanostructure technology motivated Luna-Acosta et al.`""`"` to
study transport phenomena in mesoscopic channels. For the universality in the
quasiperiodic route to chaos see Dixon et al.,`"' for universal behaviour of Lyapunov
exponent in unstable systems see Bonasera et al.,`"` for some quantum-classical
correspondence in chaotic systems see Pattanayak and Brumer`"` and for complexity
of quantum chaos see Casati and Chirikov.`"" Li and Blaisten-Barojas`" have
proposed a Hamiltonian to describe the coupling between vibration and rotation in a
molecular system. The time behaviour of such a system exhibits both regular and
irregular motion for dierent energies and dierent values of the coupling parameter.
There is a dramatic manifestation of the transition between the two types of dynamics
that dene parametric regions of regular and irregular behaviour. The Lyapunov
exponent, phase portraits, Poincare sections and power spectra are calculated. The
computer simulations show that the vibrational anharmonicity favours the regular
behaviour of the system.
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4 Fluids
The instantaneous normal mode (INM) approach to liquid state dynamics was pres-
ented by Keyes.` He recalled that considerable progress in the theory of simple
liquids has resulted from the idea`` that hard spheres provide a good reference
system. The INM approach may be regarded as arising from a dierent reference
system, the harmonic solid. Theories with dierent starting points have dierent
strengths and weaknesses, and the strengths of the harmonic reference are at short
times and in supercooled liquids. In contrast, hard spheres exhibit spurious odd terms
in the time expansion of correlation functions, and the discussion of an energy
landscape which has been so fruitful for supercooled liquids is impossible with a
hard-sphere potential.
Harmonic reference theories have a distinguished history, and it is now possible to
ll in some crucial pieces missing from the earlier work, such as the distribution of
barrier heights, and construct a theory with true predictive power. Goldstein`` is
quoted` . . . the theory as formulated by Eyring is an approximate one, based on
certain assumptions as to the details of the motion of state points on potential energy
surfaces that are as yet neither theoretically derived nor experimentally proved, and
. . . whatever rigorous theory of kinetics we will someday have, processes limited by a
high potential barrier will share some common simplications of approach, and the
description will not be terribly dierent from transition state theory. In summarizing
current research in INM theory, one would not go too far wrong by saying that we
have, with contemporary analytic and simulation techniques in hand, been moving in
the directions indicated by the quotations. New results were given by Keyes` for the
general instantaneous normal mode formalism, as well as for supercooled liquids.
The behaviour of liquid water on supercooling is a subject of long-standing scientic
debate. Recently Sciortino et al.`" reported a molecular-dynamics study of the
self-dynamics of water molecules in deeply supercooled liquid states. They found that
the decay of single-particle dynamics correlation functions is characterized by a fast
initial relaxation toward a plateau and by a region of self-similar dynamics, followed at
late times by a stretched exponential decay. They have rationalized these results in the
framework of the mode-coupling theory, MCT, for supercooled liquids.
MCT for supercooled liquids is a theory that takes into account the cage eect,``
which is associated with a transient trapping of molecules on lowering the temperature
or on increasing the density. The microscopic density uctuations of locally disordered
high-temperature and low-density uids tend to relax rapidly on the timescale of a few
picoseconds. Upon lowering the temperature or increasing the density of the liquid,
there is a rapid increase in the local order surrounding the particle, leading to a
substantial increase of the structural relaxation time. In the supercooled or dense
liquid regime a trapped particle in a cage can migrate only through rearrangement of a
large number of particles surrounding it. In this sense there is a strong coupling
between the single-particle motion and the density uctuations of the uid. See also
Fuchs`' and Kob and Andersen.``
The authors`" related the apparent anomalies of the transport coecients in water
on lowering the temperature to the formation of cages and to the associated slow
dynamics resulting from the presence of long-lived molecular cages. The so-called
critical Angell temperature in supercooled water could thus be interpreted as the
124 A. Plonka
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kinetic glass transition temperature, relaxing the need of a thermodynamic singularity
for the explanation of the anomalies of liquid water.
It was reported that water at 150 K is thermodynamically not connected to normal
water by a continuous and reversible path in terms of Gibbs free energy.`` To
determine the merits of the conjecture for a distinct phase of liquid water below 160 K,
and of its computer simulation by Tanaka,`" the dielectric relaxation times of pure
bulk water and pure water sequestered in the pores of various polymer matrices were
examined by Johari.``" The new data, combined with the literature values, show that
the molecular kinetics of pure water at 273 K is connected by a continuous path with
that of sequestered water at 160 K and below. This nding seems to remove the basis
for the conjecture of a distinct phase of water in the 136160K range, and for its phase
transformation to normal water in the 160230 K range.
Arkhipov and Ba ssler`` have presented an analytic treatment of cooperative eects
in supercooled liquids within the framework of a random-walk model describing the
dynamics of structural units in energy space invoking dipoledipole coupling. It
predicts the existence of cooperatively rearranging regions that expand as T ap-
proaches a critical temperature T
'
, identied as the Kauzmann temperature at which
the congurational entropy vanishes. However, the completely ordered state is realiz-
ed at innitely slow cooling rates only. Otherwise a kinetic freezing eect intervenes
that is responsible for the occurrence of (i) the calorimetric glass transition above T
'
and (ii) the formation of ordered and disordered regions that persist at TT
. The
proposed model predicts susceptibility spectra as well as the T-dependence of the
average relaxation frequency consistent with experimental data. The model was ext-
ended``` to supercooled melts. For the random walk model of anomalous relaxation
see also Yonezawa et al.```
Roland and Ngai``" have analyzed the short-time viscous and density relaxation in
glycerol and o-terphenyl in terms of the coupling model of relaxation.``` The model
asserts a short time decay given by exponential
S
''
exp( t/t
'
), t t
(106)
This fast : process describes the dynamics before intermolecular cooperativity has
begun to inuence the relaxation; thus, t
'
is referred to as the non-cooperative
relaxation time. At longer times, the onset of chaos at t Pt
begins to retard the

relaxation rate, whereby the correlation function exhibits a transition to the stretched
exponential form written as
S
''
exp[ (t/t*)@], t t
(107)
where t* is the intermolecularly correlated relaxation time. From eqn. (106) and (107)
the continuity condition of S
''
gives
t* (t@
t
'
)@ (108)
which, together with the fact that the crossover time, t
, is independent of temperature,
enables the temperature dependence at short times to be related to that at longer times.
The apparent activation enthalpies E
^
and E*
^
of, respectively, t
'
and t*, dened by
olnt/o(1/RT), are related as
E
^
E*
^
[ (109)
In supercooled liquids at temperatures above T
, Arrhenius temperature dependencies

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are uncommon, so that the apparent activation enthalpies are temperature dependent.
The spectral shape of the :-process in supercooled liquids was revisited by Kudlik et
al.``' Oguni``` has proposed a model for the :-relaxation process in supercooled
liquids and glasses which distinguishes between a structurally correlated region (clus-
ter) of molecules and a unit of molecules for rather independent, correlated rearrange-
ment motion. The essential aspects of the model are that the :-process is due to
rearrangement of one or a few molecules within the cluster, while essentially the same
motion in the space between the clusters is responsible for the [-process. The model
leads to the following expectations: (i) absence of divergent behaviour of :-relaxation
times at non-zero temperature (e.g. the Kauzmann temperature), (ii) close agreement
between transition temperatures, T
, for the :-relaxation in liquid and crystalline

phases of the same composition, and (iii) the possibility of crystal nucleation proceed-
ing much below T
; evidence for the latter two is presented. For a hierarchically

constrained dynamic model of relaxation see Gusarov and Volchek.```
Single electron properties in bulk uids were reviewed by Chandler and Leung.``"
The geometrical perspectives were stressed.
Solvation dynamics
Pepin et al.``" reported the observation of a continuous spectral shift in the solvation
kinetics of electrons in neat liquid deuterated water. Numerous experimental and
theoretical studies are quoted which have been devoted to elucidate the physical
mechanisms underlying the solvation of electrons in polar liquids. In the case of
electron solvation in water, the molecular relaxation time is so fast (less than 1 ps) that
its direct observation only became feasible with the advent of femtosecond pulsed laser
photolysis. Multiphoton ionization of neat liquid D
`
O at room temperature (295 K)
with 2 eV sub-picosecond laser pulses was used to study the solvation of electrons in
this medium. The set of 20 measured kinetic traces covered a wide range of probing
wavelengths (4501450nm), which allowed the authors to obtain a global picture of
the spectral changes that accompany electron hydration. The construction of transient
absorption spectra from a proper normalization of the kinetic traces conrmed the
well known existence of two absorbing species, one weakly bound, absorbing chiey in
the infrared, and a strongly bound one whose spectrum at long times is that of the well
characterized hydrated electron. The transient spectra also revealed the occurrence of
a stepwise transition between these two species as well as a concomitant continuous
blue shift of the strongly bound electronsolvent conguration. A non-linear t
performed simultaneously on all the data allowed the estimation of the characteristic
kinetic and spectral parameters of their previously proposed hybrid model of electron
solvation when it is applied to D
`
O. The global t closely matched the data for the 20
dierent probing wavelengths investigated. The electrons were trapped in
0.16_0.02 ps, whereas the stepwise transition and the continuous blue shift character-
istic times were 0.41 _0.02 and 0.51 _0.03 ps, respectively. The extent in energy of the
monoexponential blue shift of the strongly bound electron spectrum was
0.34_0.02 eV, a value which is very similar to that found for electron solvation in
methanol. Finally, it was estimated that about 34% of the electrons are directly
trapped into the strongly bound state.
For the theory of ultrafast transient absorption spectroscopy of the hydrated
electron see Bratos and Leicknam,`` and for the theory of pumpprobe spectroscopy
126 A. Plonka
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of photoinduced charge separation processes in solution Yang and Sheu``` and
Bratos and Leicknam.```
A picosecond study of the non-exponential solvation dynamics of 4-aminoph-
thalimide has been performed by Harju et al.``" in a series of n-alcohols and some
polar non-protic solvents. The results suggest single-exponential solvation dynamics
in tetrahydrofuran and non-exponential dynamics in n-alcohols. The short component
observed in n-alcohols is shorter than the longitudinal dielectric relaxation time of the
solvent, but the average solvation time is equal to it. The short solvation time is
assigned to solvent restructuring in the proximity of the excited solute molecule.
Solvent restructuring should be associated with internal rotations, such as hydroxyl
rotations of solvent molecules, rather than solvent reorientation. The long component
of the correlation function may have its origin in the solute rotational reorientation.
The role of the adiabatic intramolecular proton transfer reaction in the solvation
dynamics of 4-aminophthalimide was discussed.
Molecular dynamics simulations were used by Olender and Nitzan``` to study
solvation and solvation dynamics of a classic charge in a series of ethers of increasing
molecular weights, CH
`
(CH
`
OCH
`
)
L
H with n 1, 2 and 4. Equilibrium structures of
the solvated species, ion mobility, linear response solvation functions and non-equilib-
rium solvation were studied and compared with the corresponding results for a simple
(Stockmayer) uid. For a typical positive ion, Na>, solvation in these systems was
found to belong to the non-linear response regime; the nonlinear behaviour was
associated with the specic binding of the cation to the negative oxygen sites. Solvation
dynamics in the timescale studied (t 0.5ns) was found to be essentially bimodal, with
a short component similar in duration and magnitude to that found in simpler
solvents. However, except for the simplest systemstudied (ethyl methyl ether) the short
time component was not Gaussian (i.e. its Gaussian part is limited to insignicantly
short times) and cannot be interpreted as inertial free streaming of solvent molecules in
the potential eld of the solute. Instead the authors suggest that it originates from
damped solvent vibrations about solvent inherent structures. The character of the
solvent motions that drive the solvation process changes as the molecular size in-
creases: from overall molecular rotations in the monoether, to intramolecular segmen-
tal motions in the larger solvents. It is suggested that solvation dynamics (studied, e.g.,
by laser-induced uorescence) can be used as a probe for the dynamics of such
segmental motions in polymer electrolytes. For reconstructing the solvation time
correlation function from the time-dependent uorescence Stokes shift see Harju et
al.``'
Transient dispersions in solvation dynamics were discussed by Richert and
Richert.``` They have represented the ensemble averaged decay pattern u(t) in the
general form
u(t)
`
"
g(t)(t)dt (110)
with
u(t) exp[ (t/t
'``
)@
'``
] (111)
and
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(t) exp[ (t/t)@
"
] (112)
for
0 [
'``
O[
"
O1 (113)
Various degrees of non-exponentiality intrinsic in each relaxor, as measured by [
"
,
translate into dierent values for the time dependent dispersion o`(t) regarding the
spatially varying quantity (t). They have presented an exact solution for o`(t) and
assessed its relation to experimental data on inhomogeneous optical linewidth, o
'""
(t),
measured in the course of a solvation process in a supercooled liquid.
Rips``` has presented a microscopic model of electron solvation in polar liquids. In
the model, the electron is localized within a spherical cavity; solvation dynamics is
represented by the contraction of the cavity. Solvent ow is described by hy-
drodynamics, and the variational polaron theory is used for derivation of the free
energy change in the cavity contraction process. The calculated electron solvation
timescale in water is found to be consistent with experimental results, and the small
isotope eect on electron solvation in water is provided.
Reaction course
Fast reversible pseudo-unimolecular reactions do not approach equilibrium in the
simple exponential fashion predicted by a chemical rate equation. Many-body eects
in bimolecular reactions have been revealed in an extensive series of Brownian simula-
tions,``" showing up to three distinct phases in the approach to equilibrium. It was
concluded that more than a century after Arrhenius it is surprising to discover how
little of chemical kinetics we really understand. It was added that a widespread
misconception is that the time course of a reaction essentially obeys an approximate
form of a rate equation, so that the main problem is to determine, from rst principles
if possible, the magnitude of the reaction rate coecients. Much current study of
chemical kinetics, from gas-phase dynamics to surface reactions, centers on under-
standing the factors governing rate coecients. While such studies are of fundamental
interest and importance, the concomitant neglect of a more rigorous and comprehen-
sive study of the time course of chemical reactions is unjustied. This statement nds
little support, as this area is developing rapidly.
Reaction-diusion problems stimulate numerous works in dierent directions. One
of them is the course of chemical reactions. It follows the remarkable discovery of
important many-particle eects.`""`" The simplest example seems to be provided`"`
by the annihilation process
AA;0 (114)
in which the A particles diuse and react by pairs on contact. Calculations taking into
account the local microscopic uctuations in the particle density give
c
^
(t) :At? (115)
cf. eqn. (33) with
: min(1, d/2) (116)
where d is the dimensionality of the system.`"` Closely connected to the annihilation
model is the coagulation model
128 A. Plonka
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AA;A (117)
Balboni et al.`"` have introduced a class of d-dimensional reactiondiusion models
interpolating continuously between the diusioncoagulation and diusionannihila-
tion models. Simon`"" has looked for similarity transformations which yield mappings
between dierent one-dimensional reactiondiusion process; see also Alemany.`"`
Martin et al.`"' and Hoyuelos and Martin`"` reconsidered the eects of reaction
probability P, 0 PO1, on the pattern of annihilation and coagulation. Lee`"`
analysed the diusion-controlled reaction
kA;0 (118)
for which the reaction pattern is strongly dependent on uctuations in dimensions
d Od
2/(k 1) (119)
Asymptotically, relation (115) was recovered. According to Oshanin et al.`"" the most
pronounced deviations from the predictions of standard approaches are for the
irreversible recombination
AB;0 (120)
For equal mean initial concentrations c
^
(0) c
"
(0) the classical kinetics
c
^
(t) c
"
(t) :t (121)
is obeyed only when the concentrations are homogeneous at all times due to ecient
stirring. Under diusional stirring the reaction follows at long times the relation
c
^
(t) c
"
(t) :c`
"
(Dt)? (122)
with : d/4 for d O4, an expression which can be contrasted to the conventional
Smoluchowski-type forms
c
^
(t) c
"
(t) :1/k
''
t for d 3 (123)
c
^
(t) c
"
(t) :log(Dt)/Dt for d 2 (124)
and
c
^
(t) c
"
(t) :1/(Dt)` for d1 (125)
where D denotes the diusion coecient of the A and B particles (for simplicity taken
to be the same) and k
''
is an eective rate constant depending both on D and on the
reaction probability. For time-dependent rate coecients from Brownian dynamics
simulations see Potter et al.``" In fact, due to the sensitivity of the reactions on the
mixing procedure, qualitatively dierent kinetic patterns show up. Recently Reigada et
al.`` have investigated the eects of stirring on the kinetics of reaction (120) under
stoichiometrical conditions in two dimensions. They considered both a steady eddy-
lattice ow and a random ow mimicking turbulence. In both situations complex
decay patterns were detected. Only an intermediate stage of the reaction is dominated
by mixing. The long-time behaviour shows uctuation-dominated kinetics, c(t) :
t`, governed by eective diusion. For the case of an eddy-lattice ow a very slow
intermediate regime emerges, c(t) :t", which is associated with the closed topology
of ow lines. See also Reigada et al.```
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It is stressed`"" that the behaviour of relation (115) is mainly due to statistical
aspects, proven rigorously by Bramson and Lebowitz.`````" Subsequent works are
quoted`"" to be focused on more general situations, by including stoichiometric and
non-stoichiometric, or geminate initial conditions, the possibility of the backward and
side reactions, dierent diusion coecients for dierent species, the inuence of
stirring, change of Euclidean for non-Euclidean (fractal) systems. The references given
are supplemented by those that follow: Mai et al.```
``` on the surface reaction model

A
`
B
`
;0; Kuzovkov et al.``` on the eect of reactant spatial distribution in the
AB;0 reaction kinetics in one dimension with a Coulomb interaction; Kuzovkov
et al.``" on the eects of non-equilibriumcharge screening; Krapivsky`'" on diusion-
limited annihilation with initially separated reactants; Ispolatov et al.`' on two-
species annihilation when all particles undergo strictly biased motion in the same
direction and with an excluded-volume repulsion between the same species particles;
Janowsky`'` on a somewhat similar topic; Howard and Cardy`'` on AB;0
reaction in the steady state where xed currents of A and B particles are maintained at
opposite edges of the system; Clement et al.`'" on reaction on a catalytic surface with
two monomer reactants A and B whose reaction product leaves the surface; Hoyuelos
et al.`'` on reaction kinetics with separated reactants in one dimension when currents
of Aand Bparticles are directed towards each other; Zanette`'' on annihilation of two
diusive species on an anisotropic substrate; Sancho et al.`'` on reaction AB;0 in
two dimensions for dierent initial distributions of reactants; Koza`'` on initially
separated reaction-diusion systems with arbitrary diusion constants; Reigada et
al.`'" on spatial correlations and cross-sections of clusters in the AB;0 reaction,
Reigada et al.``" on kinetics of the AB;0 reaction under steady and turbulent
ows; Lee and Cardy`` on scaling of reaction zones and a renormalization group
study``` of the AB;0 reaction; Oerding``` on annihilation in a random velocity
eld; and Garza-Lopez et al.``" on a surcial process in which a diusing, tumbling
dipole A reacts (eventually and irreversible) with a stationary target dipole B. Most of
the quoted works have been conned to low-dimensional systems. It is therefore
important to note the work of Lin et al.``` on non-classical kinetics in three dimen-
sions, and the work of Alemany``' on a fractal-time approach to dispersive transport
in single-species reactiondiusion.
In the last few years the interest has been seen`"" to shift to systems in which the
reaction is accompanied by a steady inowof reactants. The silent feature is that under
certain conditions the reaction never reaches a steady state, cf. Mai et al.``` Oshanin et
al.`"" have analysed the kinetics of the irreversible AB;0 reaction in situations
appropriate to electrolyte solutions. They have considered diusing species which
experience short-range repulsive (attractive) interactions between like (unlike) particles
and have highlightedthe role of uctuations in the particles spatial distributions. They
have focused mainly on one-dimensional systems and devised a many-particle descrip-
tion of the reaction kinetics. They have shown analytically that the interplay between
the spatial uctuations and the interactions between the particles gives rise to a large
variety of temporal patterns. For the case of batch reaction in one dimension the mean
concentration follows rst the dependence c(t) :t`, which then crosses over to the
asymptotic pattern c(t) :t". Under a steady input c(t) grows as t` for long times.
All these regimes were also found in the numerical simulations of systems in which the
particles diuse, interact via truncated exponential forces and react on contact. For
130 A. Plonka
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exponents appearing in heterogeneous reaction-diusion models in one dimension see
Monthus;``` for scaling exponents for a ternary A2B;C reactiondiusion sys-
tem see Yen and Kopelman;``" for non-classical kinetics and reactant segregation in
d-dimensional tubular spaces see Kopelman et al.;``" for a two-species annihilation
model in one dimension in which the like particles coagulate on encounters and move
as clusters see Privman et al.;`` and for memory eects in diusion-controlled
reaction in one dimension see Sokolov and Blumen.```
All these ndings supplement the original idea`""`" that, in the course of the
AB;0 reaction, density uctuation increase and a segregation into A-rich and
B-rich areas may take place. As a result, the AB;0 reaction occurs only at the
boundaries of the segregation domains, which slows down the reaction progress in
comparison with c(t) :t following from the mean-eld rate equation said some-
times to be a naive approach to kinetics in condensed media. Lee and Privman``` have
introduced a model of three-species two-particle diusion-limited reactions
AB;A, or B, BC;B or C, and CA;C or A, with three persistence
parameters (survival probabilities in reaction) of the hopping particle. They have
considered isotropic and anisotropic diusion (hopping with a drift) in one dimension.
They have found that the particle density decays as a power law for certain choices of
the persistence parameter values. In the anisotropic case, on one symmetric line in the
parameter space, the decay exponent varies monotonically between the values close to
1/3 and 1/2. On another, less symmetric line, the exponent is constant. For most
parameter values, the density does not follow a power law. They also calculated
various characteristic exponents for the distance of nearest particles and domain
structure. Their results support the recently proposed possibility that one-dimensional
diusion-limited reactions with a drift do not fall within a limited number of distinct
universality classes.
Molecular scale diusion contributes to segregation phenomena. Strange kin-
etics``` associated with larger-scale, non-Brownian motion, might lead to desegrega-
tion and validate the mean-eld rate equation asymptotes. Zumofen et al.``"``` have
investigated mixing by Le vy ights and walks performed by the reacting species,
namely motion over many scales resulting in an enhanced diusion behaviour. For
Le vy walks with the number of steps distributed as P(n) :nA, n 0, 1 2,
they have demonstrated that segregation disappears in three dimensions for 3/2.
Oliva and Zanette``' have shown that Le vy-walk hyperdiusion, in which diusing
particles run over all the points of their trajectories, can enhance the kinetics of
one-species bimolecular annihilation and coagulation. Simple probabilistic arguments
indicated that the asymptotic particle number decay goes as n(t) :tA, with the Le vy
exponent 0 2. Therefore, for 1 those reactions proceed faster than
n(t) :t. These results were validated by numerical simulations. See also Zanette.```
For ballistic annihilation kinetics of single species in one dimension see e.g. Krapivsky
et al.``` and Ben-Naim et al.;``" for synchronous dynamics (simultaneous hopping of
all particles) see Privman.`"" Fluctuation eects in a two-species reactiondiusion
system with three competing reactions were studied by Howard.`" Kinetics of many-
species systems with aggregation of similar species clusters and annihilation of oppo-
site species clusters was discussed by Ben-Naim and Krapivsky.`"` Rich kinetic
behaviour was seen in all these studies. (See also Cadilhe et al.`"`)
As noted by Blumen et al.`"" the model chemical reactions are very specic objects
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of study, since despite their simply structured rules of game they display very rich
temporal patterns of behaviour. Fromthe point of viewof simulations, model chemical
reactions present the important advantage that in several particular cases exact
solutions (or at least, asymptotic behaviours) are known; this provides then an excel-
lent test for the numerically obtained results. On the other hand, analytical approxi-
mations may be quite misleading, when pushed beyond their (often poorly known)
limits of validity. In several, very important instances, computer simulations have
played a decisive role in showing that well established patterns of thought were
incorrect. In many cases the plotted results of simulations are intuitively easy to grasp;
this has helped very much in establishing new ways of understanding the underlying
phenomena. This seems be the case for Monte Carlo simulation study of recombina-
tion dynamics in solution reported by Kim et al.`"` Mai et al.`"' have considered the
irreversible AB;2A autocatalytic reaction via Monte Carlo simulations in one
dimension. Contrary to mean-eld-type predictions, the simulations show that only a
unique, stable front propagates. Its structure is time-independent, and the spatial
correlations turn out to be universal functions of the dimensionless interparticle
distances. These ndings are due to the discrete character (particles) of the model and
to the one-dimensional topological constraints. The temporal changes of the averaged
front form stem from velocity uctuations and are not a sign of unstable propagation.
The reaction scheme, written symbolically as AB;B, might have`"` the follow-
ing physical interpretation: species B deactivates species A but remains itself invari-
able. When reagent B is taken in large excess, this scheme is valid even if species B
undergoes conversion due to chemical reactions. Commonly adopted terminology in
analysing the processes of this type consists in designating species A as Brownian
particles (with regard for the diusion nature of their motion) or, for brevity, simply as
particles, and species B as traps. In the most practically important situation, when the
traps are xed, describing the kinetics of processes AB;B reduces to a solution of
the problem of Brownian-particle survival on randomly distributed traps. It is recal-
led`"` that in the initial problem underlying the traditional theory of diusion-
controlled processes, the traps were assumed to be ideal adsorbing spheres evenly
distributed in space. This was the model suggested and analysed for the rst time by
Smoluchowski.`"` His approach to nding the survival probability of a particle
randomly walking among these traps was based on the single-particle approximation
that does not take into account competition of the traps for the opportunity to react
with the particle. Makhnovskii et al.`"` have analysed the eect of spatial correlations
between traps on the kinetics of Brownian-particle capture. Amodel in which the traps
are grouped to form clouds, which are statistically similar to each other and are
distributed in space randomly, was suggested and discussed. A general formula for the
probability of particle survival was derived. It follows from this formula that the trap
grouping always results in retardation of the trapping process, irrespective of how the
group clustering occurs. The trapping deceleration depends signicantly on the cloud
structure. The eect considered was scrutinized for a particularly important case of
non-overlapping clouds. At asymptotically long times, the cloud structure becomes
unimportant, and the decay kinetics is described by a universal dependence similar to
the well known ZeldovichOvchinnikov uctuation asymptotes in which the cloud
concentrationstands for the trap concentration. The eects due to the state of mobility
of each of the species are discussed by Berezhkovskii and Weiss.`"" As recalled,"""
132 A. Plonka
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Blumen et al."" have considered the survival probability of one A and several B
particles such that the A particle is annihilated at the encounter of the B particle.
Depending on which of the species performs the motion, there is a distinction between
the trapping (only Aparticles move), the target (only Bparticles move), and the moving
target (both species move) models. Re et al.""" and Caceres et al.""` have generalized
the target model to allow an encounter of A and B particles without annihilation
depending on the internal state of particle B. Only if the particle designated as the trap
is active, annihilation will take place. If the trap is inactive it behaves as a regular site.
This problem is seen""" to be related to that of particles diusing in the presence of a
gate that opens and closes at stochastic times.
Conformational uctuations of a macromolecule or a ligand seem to play a signi-
cant role in determining the kinetics of ligand binding. Aclassical example quoted""` is
that of the entrance of oxygen into the heme pocket of myoglobin. In the static X-ray
structure of myoglobin there is no hole for the ligand to enter and it was suggested"""
the side chains blocking the entrance might act as a gate which has to swing out to
admit the ligand. Thus, in the simplest case, the gate has two states: an open state
representing a reactive conformation and a closed state representing a non-reactive
conformation. Zhou and Szabo""` have studied the kinetics of the irreversible diu-
sion-inuenced reaction between protein (P) and a ligand (L) when [L] [P] and the
reactivity is stochastically gated due to conformational uctuations of one of the
species. If gating is due to the ligand they have shown that the Smoluchowski rate
equation, d[P(t)]/dt k(t)[L][P(t)], can be generalized by simply using a stochasti-
cally gated time-dependent rate coecient, k
'
(t). However, if gating is due to the
protein, this is no longer true, except when the gating dynamics is suciently fast or the
ligand concentration is very low. The dynamics of all the ligands around a protein
becomes correlated even when the ligands diuse independently. An approximate
theory for the kinetics of protein-gated reactions that is exact in both the fast and slow
gating limits was developed. In order to test this theory, a Brownian dynamic simula-
tion algorithm based on a path-integral formulation was introduced to calculate both
k
'
(t) and the time dependence of the protein concentration. Illustrative simulations
using a simple model were carried out for a variety of gating rates. The results are in
good agreement with the approximate theory. (See also Berezhkovskii et al.""`) For an
electron transfer model for the electric eld eect on quantum yield of charge separ-
ation in bacterial photosynthetic reaction centers see Tanaka and Marcus,""' and for a
model for dynamic protein control of energy transfer to photosynthetic reaction
centers see Trinkunas and Holzwarth.""`
Eisenberg et al.""` described the stochastic trajectories that underlay classical
diusion between known concentrations. Their work started as an attempt to describe
the stochastic motion of ions through single biological channels, protein molecules
that open to form a pore allowing ions to move across a cell membrane. As noted by
these authors, this is the same problem that motivated Fick, who was both a physiol-
ogist and physical chemist, to invent classical diusion theory.
It seems highly instructive to follow in some detail the kinetics of a diusive capture
process reconsidered by Krapivsky and Redner""" under the term: lamb besieged by a
pride of lions. They have considered a particle system which consists of a diusing
prey and N independent, diusing predators, with Neither nite or innite. The prey is
absorbed, or dies, whenever it is touched by any of the predators. Of interest is the
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probability S
,
(t) for this lamb surviving until time t when it is besieged by these
predatory lions. While this appears to be a simple problem, there are important
aspects of the long-time behaviour which are incompletely understood. Their resol-
ution has fundamental ramications for diusive processes in the presence of complex
absorbing boundaries and also has practical implications, as this type of capture
process appears in a variety of applications, such as diusion-controlled chemical
kinetics, wetting, melting and commensurateincommensurate transitions. It is known
rigorously that for spatial dimension d P3, the capture process is unsuccessful in that
there is a nite probability that the lamb survives indenitely for any N and for any
initial spatial distribution of lions. This result is a consequence of the transience of
random walks for d 2. For d 2, the capture process is successful: the lamb dies
with probability one. However, diusing lions in two dimensions are still suciently
poor predators that the average lifetime of the lamb is innite. In one dimension,
however, diusing lions are more ecient in their predation because of the recurrence
of random walks. This typically leads to a lamb survival probability which decays
according to a power law in time. More generally, we may consider the survival
probability, S
,+
(t) S
+,
(t), when initially N lions are placed to the left and M lions
are placed to the right of the lamb. The most interesting situation is when initially N
lions are to one side of the lamb. For this initial condition, realizations in which the
lamb runs away from the lions lead to an anomalously slow decay of the lamb survival
probability. The primary result is to determine the asymptotic behaviour of the lamb
survival probability in this predatory environment, S
,"
(t) YS
,
(t). For nite
N, S
,
(t) :t@
,
with [
,
:lnN, while S
`
(t) :exp( ln`t) for N;-. These depend-
encies arise from the fact that the motion of the closest lion (whose individual identity
can change with time) is enhanced compared with normal diusion. When the number
of lions is nite, this enhancement manifests itself in the diusivity of the last lion being
proportional to lnN. This factor is ultimately responsible for the logarithmic increase
of [
,
on N. In the limit N;-, the coordinate of the last lion actually varies as
(tlnt)`, and leads to the lamb survival probability varying as exp( ln` t). For
diusion and trapping on a one-dimensional lattice see also Giacometti and
Murthy,"" Sanchez et al." and Sanchez and Wio;"` for some universal scaling for
diusion-controlled reactions among traps see Torquato and Yeong."`
In recent years much eort has been devoted to the theoretical study of liquid-phase
reversible diusion inuenced reactions, cf. Gopich and Doktorov."" The kinetics of
reversible energy transfer was discussed by Burshtein and Lukzen;"` reversible excit-
ed state processes were examined by Molski and Boens."' Long-time behaviour of the
observables in irreversible reactions in liquid solutions was studied by Kipriyanov and
Doktorov."` Non-Markovian theories based on two commonly used many-particle
approaches to the derivation of kinetic equations of elementary bimolecular reactions
in diluted liquid solutions were analysed by Kipriyanov et al."`
"`" Traytak"`
discussed the diusive interaction in diusion-limited reactions; Martinez"`` analysed
the kinetics of non-stationary, single species, bimolecular, diusion-inuenced irre-
versible reactions; and Sposito"`` has analysed the scaling invariance of the
Smoluchowski law. Naumann and Szabo"`" have compared the Smoluchowski ap-
proach with some alternative approaches to diusion-inuenced uorescence quench-
ing. Excitation transfer reactions were discussed by Sumi;"`` spatially non-local eects
in rapid chemical reactions were discussed by Molski et al.;"`' Burshtein and Fran-
134 A. Plonka
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tsuzov"`` have described the interplay of geminate and bimolecular reactions in
multistage electron and energy transfer; and Burshtein and Sivachenko"`` have dis-
cussed the role of excitation lifetime in electron transfer reactions in solutions.
The recombination reaction of radicals photolytically produced in solution pro-
ceeds via two distinguishable kinetic phases. At short times recombination between
geminate radicals predominates, while at long times recombination between non-
geminate radicals, that have diused away from their geminate counterparts to the
bulk solution, takes place. In most theories dealing with the eect of added scavenger
molecules on the radical recombination reaction, only the geminate recombination
phase has been considered. However, if the concentration of radical pairs generated is
high, the interplay of bulk recombination in the dynamics needs to be considered. Kim
et al."`" have formulated a theory that deals with the scavenging eect in both the
geminate and bulk recombination phases within a unied framework. They have
shown that the scavenger concentration C
'
and the scavenging rate coecient k
'
have
independent eects on the reaction, in general. In contrast, conventional theories
involve two quantities only as a product k
Q
C
Q
, usually in the form of a Laplace
transformation variable. For diusion eects on geminate charge recombination see
Yoshimori et al.,"`" who have investigated the intermolecular electron transfer system.
Analytical and numerical calculations are presented for reactiondiusion equations.
In some limiting cases of the equations, a condition is establishedwhere the population
of geminate ion pairs decreases exponentially by charge recombination. This condition
is that the ion pairs are produced inside the zone of recombination and charge
recombination takes place before ion pairs diuse into separated ions. Numerical
calculations are made in realistic cases where reorganization energy in the expression
of the rate constant depends on the reactant distance. As a result it is found that the
population of ion pairs has both components of exponential decrease and a root
inverse tail (t`). The component of exponential decrease is large when the recom-
bination is fast.
To enter the discussion on viscosity dependence of rate constants in uids it seems
enough"` to recognize t
"
in relation (9) as the relaxation time of the conformational
uctuation of the reactant system. Then, if these uctuations are driven and/or
damped solely by thermal motions of solvent molecules through friction, t
"
should
simply be proportional to viscosity p. Hence, from eqn. (10) one gets
k :t? :p?
k :p?
for 0 : 1
for a 1 :
(126)
i.e. the form desired to t the experimental data for the rate constant dependence on
solvent viscosity. Despite this simplicity in the derivation of relation (126), there are
some important implications of the model worthy of discussion, especially in compari-
son with some more elaborated approaches used recently. Of special interest are the
works of Sumi,"``
"`` who aimed to provide a general expression for a rate constant

dependent on the thermalization time t in the reactant system for reactions limited by
electron, proton, or atom-group transfer. He found Kramers theory" and some of its
modications to be inapplicable. The main objections are that these theories model
chemical reactions as a diusional surmounting of a potential barrier by a Brownian
particle in a double-well potential. They cannot be valid for reactions whose rate-
limiting step is electron or proton transfer occurring by quantum-mechanical tunnell-
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ing, even at room temperature, or for reactions whose rate-limiting step is atom-group
transfer, since it usually occurs by a ballistic jump of atoms over a potential barrier
rather than by a diusional surmounting. Besides, in these theories in the high-friction
limit one has
k :t (127)
leading to relation (126) depending on the relation between t and p. Sumi"`` consider-
ed the case of reaction coordinate composed not only of intramolecular or atomic
vibrational motions but also of conformational uctuations of the system itself, driven
by thermal motions of solvent molecules. These uctuations were assumed to be
describable in terms of Brownian motions. Their relaxation time t, regarded as
proportional to the viscosity p of the solvent, is much longer than periods for the
vibrational motions. It was shown that when reactant populations follow a single-
exponential decay after a time of order t, in exothermic reactions the rate constant k
'
tends, irrespective of initial conditions, to the inverse of the rst passage time for
initially thermalized reactants. The rate constant k
'
was expressed as
k
'
1/(k
k
'
) (128)
where k
is the thermal equilibrium rate constant of the usual theories, such as

transition-state theory, and k
'
is the uctuation-limited rate constant decreasing with
increasing t or p. For
k
v exp( AG
/kT) (129)
where AG
is the free energy of activation and v is the frequency factor at temperature

T, k
'
was shown to be
k
'
:t?v?exp( AG
/kT) (130)
where 0 a 1 and 0 1 are positive constants. Assuming that 1/ in eqn. (9)
depends on T in a similar way [eqn. (129)], one gets
k :t?v?exp( :AG
/kT) (131)
which because of a 1 : [cf. eqn. (126)], seems to be similar to relation (130). The
dierence between relations (130) and (131) is not so great in the presence of two
positive constants in expression (130), both of which are model dependent, and in the
SumiMarcus model"`' both depend on the ratio of inner-sphere reorganization
energy z
'
to the out-sphere reorganization energy z
a : 1 z
'
/z
for z
'
/z
or 2 z
'
/z
"
1 (132)
:1/(1 z
'
/z
) (133)
The main dierence between these relations is in their potential applicability. It is
said"`` that we get k
'
5k
'
fromrelation (128) when in the large tv limit, i.e. for t in
our notation, k
'
k
. In contrast, eqn. (131) applies only for the limit t, and this is
the limit in which one nds for some reactions, including the biochemical ones, that
rate constants do depend sublinearly on viscosity. It was said that we remove this
dependence in the small tv limit, t in our notation, when k
k
'
. Then from eqn.
(128) k
'
5k
, covering the results of the usual theories. In our approach for t there
is no constant specic reaction rate, i.e. the rate constant, and the kinetics is dispersive,
136 A. Plonka
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cf. eqn. (7). Therefore one needs quite another way to remove the viscosity dependence
in relation (9). The obvious way in our approach is to reconsider the implicit assump-
tion of a random-walk modelling of reaction kinetics for very reactive intermediates.
The implicit assumption is this: we are modelling reactions with high local reaction
probability, P, when two reactants collide. In general, for P;1 there is diusion-
limited reaction kinetics, while for P1 one has reaction-limited kinetics. This means
that only for P;1 is eqn. (9) valid. The lower the numerical value of Pthe closer to 1 is
the apparent numerical value of : seen in computer simulations performed by Shi and
Kopelman"`` for bimolecular reactions in one dimension, on a two-dimensional
square lattice, on a two-dimensional critical percolation cluster, and in three-dimen-
sional cubic lattices with various local reaction probabilities. This is the way to get
k b/ fromeqn. (7), which covers the result of usual theories. For Brownian dynamics
simulations of diusion-controlled reactions with nite intrinsic reactivity see Gupta
and Khakhar."``
For chemical reactions in solutions which are close to, but slower than the diusion-
controlled limit it is usual to describe the reaction step using the radiation boundary
condition, a simple parametrisation which treats rst encounters and re-encounters
identically. Green et al."`" have introduced a new stochastic description of partly
diusion-controlled reactions which retains the diusion equation but attempts to
model the way in which the reactivity of a pair grows back as a function of time since
the last unreactive encounter. Analytic solutions for the new formalism were given for
several important cases. The correction of the rate constant from the diusion limit
was shown to depend on the diusion coecient in an entirely dierent way from the
usual parametrisation using the radiation boundary condition. The theory was ap-
plied to the reaction between the solvated electron and oxygen in aqueous solutions.
Relation (128) has a general form of the rate constant for the consecutive two-step
mechanism of reaction. In our formalism this kind of approach is not used, as in a
general case [cf. eqn. (7)] we assume that the reactions proceed on many timescales.
This is consistent with an interpretation of the dispersive kinetics in terms of fractal-
time rate processes. This allows us not to enter the discussion on thermal and
non-thermal equilibrium forms during the reaction.
Barzykin and Tachiya""" reviewed some recent advances in the theory of reaction
kinetics in microdispersive systems with an emphasis on self-organized molecular
assemblies such as micelles or microemulsions and their clusters. They have paid
particular attention to various deactivation processes of excited states, including
uorescence quenching. Principal models used for the analysis of uorescence decay
proles in systems with restricted geometry were also discussed by Lianos."" Much
emphasis is given by him to a universal model of stretched exponentials and its
applications for the study of diusion-controlled and resonance energy transfer
quenching. The eld of supramolecular photochemistry was reviewed by Turro.""`
Moreno et al.""` have studied the stochastic eects on the time-dependent rate
constant of photodimerization of 12-(9-antroyloxy)stearic acid in micelles; Almgren et
al.""" have reported the uorescence quenching studies of micellization and solubiliz-
ation in uorocarbonhydrocarbon surfactant mixtures; and Szajdzinska-Pietek et
al.""` have reported on uorescence studies of the self-assembly of poly(ethylene-co-
methacrylic acid) ionomers in aqueous solutions. For kinetics of micelle formation see
Telgmannand Kaatze""'""`. Dynamic light scattering and ultracentrifugationstudies
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performed by Hidi et al.""` have shown that, in aqueous solutions of some anionic
surfactants such as sodium dodecyl sulfate (SDS), poly(vinyl acetate) (PVAc) latex
particles swell up to 60 times their original volume. The process is reversible on
dilution. This unexpectedly large swelling always commences at a surfactant concen-
tration below the critical micelle concentration, e.g. at 4.5 mmol dm` for SDS. The
swelling rate is best expressed by a stretched exponential. Swelling is inferred to be due
to the formation throughout the particle of polymermicelle complexes, the structure
of which is similar to those reported in systems containing certain water-soluble
synthetic polymers and surfactants. The swelling is reversible, and on dilution the
particles contract rapidly to slightly less than their original size. The dierence is due to
escape of some lower molecular weight material from the particles. The reversibility
shows that a degree of morphological integrity of the particle is preserved on swelling.
This is attributed to the existence of microdomains of intrinsic entanglements, prob-
ably formed during the original emulsion polymerization process.
Molecular dynamics during linear chain polymerization from real-time dielectric
spectrometry and calorimetry has been discussed by Tombari et al.""" During the
process of polymerization, molecules in the initially molecular state of a liquid com-
bine chemically to form bigger molecules. The product, which is obviously bigger in
size than the reactants, diuses at a slower rate than either of the reactants. This causes
the rate of chemical combination to become slower. Hence, any further chemical
combination that occurs is aected by this slower rate, and, after the combination has
occurred, the product is a yet bigger macromolecule, which diuses even more slowly.
This continues until both the diusion and the chemical combination rate, after
slowing each other progressively more, become too slow to be experimentally observ-
able. At this instant, the process seems to come to a virtual halt, within the timescale of
ones observation. When the liquids viscosity has reached a certain high value, and the
diusion coecient a certain low value, the liquid is said to have vitried, almost
isothermally. This process of a negative feedback between the chemical combination
that increases the molecular size and the diusion, which slows the rate of the very
process that causes this increase in size, is usually studied as a function of time, and
explained in the reaction time domain. To gain physical insight into the molecular
dynamics of such processes, more recent studies have attempted to change the manner
in which the process is viewed, by interpreting it in terms of the number of covalent
bonds formed; these bonds increase the congurational restrictions on molecular
diusion. If this is done, the molecular dynamics of the process can be related to an
intrinsic property of the structure of the liquid, rather than to an extrinsic property
such as the time allowed for chemical combination. To gain further insight into the
physics of the process in which a negative feedback between the chemical combination
and the molecular dynamics is predominant, the authors made a detailed study of a
linear chain macromolecule during the course of its formation and growth by polymer-
ization. See also Parthun and Johari,"`" Ferrari et al.,"` Wasylyshyn and Johari,"``
and Johari."`` For dual-purpose uorogenic probe of polymerization dynamics see
Warman et al."`"
Oshanin et al."`` have studied the direct incoherent energy transfer from an immo-
bile excited donor molecule to acceptor molecules, which are all attached to polymer
chains, randomly arranged in a viscous solvent. The decay forms were found explicitly
for arbitrary conformations of polymers. See also Oshanin et al."`' Dynamic and
138 A. Plonka
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conformational properties of polyampholytes in external electric elds were discussed
by Schiessel et al."``
According to Baumga rtner and Muthukumar"`` one particular area in polymer
research is still limping behind the general peak of progress. This is the statistical
mechanics of polymers with intrinsic or external quenched disorder. One may consider
this class of problem to be divided into two parts. One is concerned with the problem
of how the structures of disordered porous solids aect the conformational and
thermodynamic properties of macromolecules. The second is concerned with the
transport properties of polymers in a porous environment. Both parts are reviewed.
See also Ebert et al.,"`" who used the renormalization group approach"'" to analyse
the center-of-mass motion of a polymer in a Gaussian disordered potential. While in
the long-time limit normal diusion was found, there was also identied a universal
short-time regime in which the dependence of the centre-of-mass motion over several
decades approximates a power law with an eective exponent that continuously
depends on disorder (and also weakly on the time interval). For diusion of a polymer
chain in a random layered ow see Oshanin and Blumen"' and Sommer and
Blumen."'`
Static and time-dependent properties of polymer gels around the volume phase
transitions were reviewed by Hirotsu."'` One of the characteristic features of a gel is
that the inhomogeneity of the network density develops quite easily during the
changes of state. Such inhomogeneities manifest themselves as various surface and
bulk patterns. Their time evolution follows a power law. Cross-linking polymers at the
sol-gel transition were found by Schiessel and Blumen"'""'` to be very good model
systems for studying power law decays. For discussion of universal self-diusion and
subdiusion in colloids at freezing see Indrani and Ramaswamy"'' and Fuchs;"'` for
probe diusion in polymers see Xia and Wang"'` and Cicerone et al.;"'" and for
diusion of electrons in quasi-one-dimensional polymer structures with random inter-
chain couplings see Xiong et al."`" The last authors"`" have studied electronic diu-
sion in quasi-one-dimensional systems with randomly placed interchain single- and
double-bond cross-links corresponding to one and two adjacent interchain hoppings,
respectively. While in the single-bond case all states are localized, for the double-bond
case many completely unscattered states are obtained, forming a dilute conducting
band which leads to superdiusive wave packet dynamics. This new type of band
structure can explain the unusual transport properties of highly conducting polymers.
See also Anglada et al."`
Fredrickson"`` has presented a theory for the diusion-controlled coupling of
end-functionalized A and B homopolymers at an AB interface. The eective reaction
rate coecient k
was shown to exhibit a surprising degree of universality associated

with the small center-of-mass diusivity of high molecular weight polymers. For
polymers below the entanglement threshold (NN
), k
scales with molecular weight

as k
:1/ln N, and above the threshold, k
:1/NlnN.
Astatistical dynamical theory of the crossover fromunentangled Rouse dynamics to
entangled behaviour was constructed by Schweizer and Szamel"`` for chain polymer
solutions and melts. Both time and spatial crossovers in long-chain uids, and the
degree of polymerization crossover for short polymers, were treated. The analysis is
based on a microscopic theory of the perturbative dynamic corrections to Rouse
theory, arising from chain connectivity and intermolecular excluded-volume forces.
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The dependences of crossover properties, such as the plateau shear modulus and
entanglement time and length scale, on solution density, solvent quality and chain
statistical segment length are derived by combining the dynamical theory with equilib-
rium liquid state integral equation methods. Scaling relations are obtained which
appear to be in general accord with most experiments on both solutions and melts. The
physical origin of the predicted scaling behaviour is the fractional power law temporal
decay of the entanglement friction memory function on intermediate timescales, and
power law reduced density dependence of the equilibrium force correlations. The
theory was also applied to compute the dependence of the chain normal mode
relaxation times on polymer density and chain length. Favourable qualitative com-
parisons with recent neutron spin echo experiments were made.
It seems proper to add that Momonaga et al."`" have presented an interpretation of
dissolution rates by fractal dimensions for particles in the size range from 50 nm to
about 5 mm. Three typical values of the dissolution fractal dimensions d
'
were distin-
guished. The dissolution behaviour of agglomerated particles (Smoluchowski par-
ticles) has a characteristic value of the dissolution fractal dimension 0 d
'
O1.
Compact particles suering vigorous Brownian motion (Brownian particles) can be
characterized by 1 Od
'
O2. Compact crystals bigger than about 10 jm show a
characteristic dissolution fractal dimension 2 Od
'
O3.
5 Solids
FluidSolid Transition
As noted by Wolynes"`` a triumph of modern theoretical physics is the notion that
rigidity and orderliness go together. A periodic array of atoms is recognizable and
globally dierent from a uid. Pushing at it in one place causes no rearrangement
because a local disturbance will be met by a collective response of the whole. The
rigidity of glass, an amorphous solid, is more mysterious. Without any apparent order,
a chaotic jumble of atoms behaves as if rigidly frozen.
Crystallization
Studies of Hage et al."`' on crystallization of metastable water were followed by those
of Johari and Sartor,"`` who have determined the crystallization kinetics of ice from
water-swollen wheat gluten. The compressed exponential, written in the form
x 1 exp[ k(T)tL] (134)
known from the theory of nucleation and growth processes developed nearly 60 years
ago by Kolmogorov,"`` Johnson and Mehl"`" and Avrami"`" (KJMA), was found to
be not adequate for simulation of DSC scans. It is not surprising, as the KJMA
equation, although frequently invoked to interpret non-isothermal DTA/DSC experi-
ments, is valid only for isothermal crystallization."` Furthermore, it is known that the
KJMA equation must be modied for certain types of isothermal crystallization
processes (cf. Ortega et al.,"`` Llopiz et al.,"`` Ryden and Wernersson,"`" Wein-
berg,"`` Zanotto,"`' Sessa et al.,"`` Erukhimovitch and Baram"`` or Todinov"`").
For water crystallization kinetics in high-protein food see Sartor and Johari,""" and
in hydrated gliadin and hemoglobin, see Sartor and Johari."" See also Johari""` for a
140 A. Plonka
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discussion on determining the temperature-invariant enthalpy change and other ther-
modynamic functions on transformation of proteins and other biopolymers.
Jenniskens and Blake""` studied in detail the structural changes that occur in the
amorphous water ice when it is warmed above the glass transition temperature.
Typically, when an ice lm was deposited from the vapour at 14 K and warmed at a
rate of 13 Kmin, cubic crystalline peaks emerged at 151 _4 K. Upon continued
warming, the intensities of the crystal diraction peaks increased until 160170K, at
which time the pattern appeared fully matured. In a similar way, they have measured
the growth of the crystalline fraction during isothermal annealing experiments con-
ducted at various temperatures. Ice layers were deposited and held at 86 K for 1 h,
heated to a point 10 K below the annealing temperature at a rate of 1 Kmin and
then heated rapidly, at 10 Kmin, to the annealing temperature in the range
125143K. Two regimes of growth of the crystallization fraction were found: a regime
of rapid initial increase and a second regime of more gradual increase. The parameters
n and k were derived from loglog diagrams of diraction intensity ln(1 x) vs.
time. They have found that n 2.0 _0.3 for the rst regime (or n 1.0 _0.3 if one
allows for an induction period). For the second regime, n 0.8 _0.3 (with or without
an induction period). These values are in good agreement with n 2.43 and n 0.90,
respectively, found by Hage et al."`' in a infrared study of amorphous ice. These
authors annealed a layer of amorphous ice for 120 min at 130 K, warmed the ice to
144 K, and measured the crystalline fraction by decomposing the 3.07 jm infrared
band into crystalline and amorphous components. In another study by these authors,
three samples studied at 140, 144, and 146 K without prior annealing did not show a
clear distinction between a rst and second crystallization regime, and gave somewhat
higher values of n 1.30, 1.34 and 1.15, respectively, perhaps because crystallization
proceeded rapidly enough to blend the two regimes. (See also Hage et al.""") The rate
coecient k was assumed to be thermally activated with an activation energy AH
given by
kL(T) kL
"
exp( AH/RT) (135)
cf. Hage et al."`'
Jenniskens and Blake""` have found an activation enthalpy of
AH39 _5 kJ mol for the rst regime and AH58 _10 kJ mol for the second
regime. By comparison, Hage et al."`' found an activation enthalpy of
AH67 _3 kJ mol for the second regime. It was noted that these values are
roughly equivalent to breaking two and three typical hydrogen bonds in ice.
Smith et al.""` have studied the molecular diusion in amorphous solid water by
measuring the extent of isotope exchange and mixing in vapour-deposited ultrathin
lms. Their results indicate there is long-range translational diusion that occurs
concomitantly with the amorphous to crystalline ice phase transition. The apparent
diusivity estimated from their data is a factor 10' greater than an Arrhenius
extrapolation for diusion in crystalline ice. This nding suggests that the amorphous
material exhibits liquid-like translational diusion prior to crystallization at tempera-
tures near 155 K. Phase transition and entropy of amorphous ices have been discussed
by Johari.""' For a facet of recent ice sciences see Suga.""`
The classical (KJMA) equation for nucleation and growth transformations, which
assumes random nucleation and cessation of growth where grains impinge, was
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originally derived by accounting for the extended volume that is obtained when
overlap of the growing grains is (mathematically) permitted. Motivated by experimen-
tal and computational results that call into question the validity of this equation and
by recent theoretical concerns about the appropriate content of the extendedvolume, a
derivation of the KJMAequation was presentedby van Siclen,""` that does not rely on
the concept of the extended volume. On the other hand, this concept was shown to be
useful by Fanfoni and Tomellini""" for describing the time dependence of the photo-
electron and/or Auger signals during the overlayer formation in the case of Vol-
merWeber growth mode, i.e. three-dimensional island formation. The impingement
among clusters has been taken into account in the framework of Avramis statistical
approach. At rst the systemhas been considered in which nucleation occurs at a given
number of pre-existing sites randomly distributed throughout the whole surface. The
results obtained by numerical computations indicate that particular conditions can be
indeed realized for which the photoelectron signal is chiey related to the kinetics of
the surface fraction that is covered by islands. A more involved system has been also
modelled where nucleation does not occur at pre-existing sites but throughout the
formation of stable dimers. Under this circumstance, Avramis treatment of island
impingement can be still retained, although now a system of integral dierential
equations has to be solved to obtain the kinetics. Such a modelling should be suitable
for describing metallic lm growth studied by a photoelectron signal. (See also Tomel-
lini and Fanfoni.`"") Examples of application of the KJMA equation to calorimetric
kinetic data on primary crystallization, for Fe
`'
Nd
'
B
`
, Fe
```
CuNb
`
Si
``
B
"
and
Al
``
Ni
`
Nd
`
Cu
`
, amorphous alloys under isothermal treatment, are given by
Clavaguera-Mora and Clavaguera.`"
The inuence of non-uniform distribution of nuclei on crystallization kinetics is
discussed by Sun et al.`"` and Uebele and Hermann.`"` The idealizations made in
formulating the KJMA equation are under current discussion. Jou and Lusk`""
developed a phase-eld model which extends the viewpoint taken in deriving the
KJMA equation to include non-isothermal conditions, anisotropy, and mechanical
eects. Finite size corrections are introduced by Levine et al.`"` Sessa et al.`"'
presented computer simulations of the rst-order phase transition visualized in real
space to give information on the morphology of the system at a microscopic level.
These simulations, for the case of random nucleation, were used to verify KJMA
kinetics. A general equation describing the transformation with a nucleation-and-
growth mechanismwas derived by Yu.`"` In his treatment, based on the calculation of
the survival probability, both the nucleation and the growth rates are allowed to vary
in space and time, and thus very broad conditions are considered. In particular, the
correlation eect between the sites can be studied by calculating the probability of the
relevant occurrences. In the simplest case of homogeneous systems, the KJMA equa-
tion is re-established.
Hoogers and King`"` have developed a model describing the stages of nucleation,
growth and saturation in two-dimensional ordering processes, based on the earlier
analysis of Avrami."`" The standard power growth law`""`"
l A(T)tV (136)
for ordered domains of linear dimension l growing from a disordered array, with x
being an universal exponent and A(T) a temperature-dependent term, turned out to
142 A. Plonka
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be a special case of this new model, which also provides an expression for the time-
independent prefactor A(T) in terms of the growth rate and density of growth
nuclei.
The time evolution of the total perimeter of clusters growing on a surface has been
described by Tomellini and Fanfoni` on the basis of the KJMA equation. A general
formula, which can be easily extended to any spacial dimension, was obtained. When
particular nucleation functions and the cluster growth law are considered, the kinetics
of the perimeter can be explicitly calculated, and moreover can be expressed as a
function of the covered surface. Experimental data on the eciency of a Cu/CuO
V
model catalyst towards imide formation have been satisfactorily described by the
model. Moreover, the growth of Ag on a GaAs(110) surface studied via photoelectron
spectroscopy has been qualitatively explained by the proposed model. In the model
case of cylindrical clusters a knowledge of the evolution of the total perimeter allows
the entire area of the lm to be evaluated. (See also Irisawa et al.``) Description of
microdomain growth in competitive three-dimensional agglomerates has been given
by Gadomski et al.`` The kinetics of pressure-induced hydration of model lipid
membranes was studied by Gadomski`" in terms of the KJMA equation and the
concept of fractal-like chemical reaction kinetics. The same assumptions were used by
Gadomski and Luczka`` to study the kinetics of a temperature- or pressure-induced
phase transformation in lipid bilayers.
For the use of the KJMA equation see also, e.g., Michaelsen et al.,`' for a recent
survey of kinetics of polymer crystallization see Long et al.,`` Arroyo et al.`` and He
et al.;`" for Avrami master curves for isothermal polymer crystallization see Lambrig-
ger.``" For limit theorems for general spatial birth and growth process see Chiu;``
and for a discussion of rst-order phase transitions see Kukushkin and Osipov``` and
Garrido and Crespo.```
Vitrication and physical ageing
There is much activity concentrated on the liquidglass transition, which may be
considered``" as the deepest and most interesting unsolved problem in solid-state
theory. Angell``` admits that not only can one not obtain an explanation of the glass
transition, but also one cannot even get a consistent answer to what is meant by the
question of how the glass transition is dened. The liquid state seems not to be
involved, cf. Suga.``'
``` The term glass transition has become generalized to cover

any system which passes from an internally equilibrated state to one in which the
particle motions are so sluggish that a time-independent state can no longer be
reached.``` The phenomenon of interest starts to be ergodicity breaking, meaning
falling out of equilibrium. Consequently, it might be better to start at the low tempera-
ture and to ask the question What is it that enables the system with rising temperature
to escape from its particular, mechanically stable, low-energy minimum and to gain
access to all the other minima within kT? In other words, what physics enables a
system to become ergodic? The often mentioned empiricisms, cf. Manseld``" and
references therein, are as follows: (1) the Kauzmannparadox,``" whichshowed that the
entropy, enthalpy, volume, etc. when plotted against temperature and extrapolated
below T
, appear to fall below the corresponding curves for the equilibrium crystal at
temperatures well above absolute zero. (2) For many liquids the relaxation time in the
vicinity of T
depends on temperature according to the VFT eqn. (48). (3) Many

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properties of supercooled liquids relax according to the Kohlrausch function. The
same is true for glasses, cf. e.g. Koide et al.`````
To the above, we have to add according to Sokolov``` the two new features of glass
transition dynamics, namely qualitative changes at a certain temperature T
above T
and the presence of excitations in the mesoscopic frequency range 101000GHz

(which is signicantly below the frequency of single-molecule vibrations) in the glass
transition scenario. (See also Quitmann et al.,``" Novikov,``` Novikov et al.``' and
Sokolov et al.``````)
During recent years, the mode-coupling theory has been developed as a model for
the dynamics of strongly interacting disordered matter (cf. Franosch et al.``"). This
theory is formulated in terms of non-linear coupling between uctuation modes and
predicts that the dynamics of glass-forming liquids should change signicantly near T
.
The change consists of decoupling of dierent relaxation processes around T
and the
appearance of an additional relaxation process, the so-called JohariGoldstein [-
process, at temperatures belowT
. For evidence of two structural relaxation processes

near the glass transition of a strong glass former see, e.g., Yannopoulos et al.`"" For a
classication scheme of strong and fragile glass formers see the previous report and the
recent discussion of Hodge,`"`"` Roland and Ngai`"` and Novikov et al.;`""`"` for
an application of the fragility concept to metallic glass formers see Komatsu.`"' Low-
temperature anomalies in strong and fragile glass formers were discussed by Sokolov
et al.`"` For structural relaxation and fast dynamics in glycerol, which is to be placed
between fragile and strong glass formers, see Wuttke et al.`"``"" Struiks law for
enthalpy retardation at the glass transition in poly(n-alkylmethacrylates), measured by
DSCageing experiments, has been discussed by Hempel et al.``" Non-exponential and
linear characteristics of the irreversible enthalpy relaxation functions in diben-
zofuranuorene solid systems and their interpretation have been discussed by Fujita
et al.``
For a discussion of glass transition singularities see also Odagaki`````` and
Odagaki et al.``" The so-called translationrotation paradox for diusion in glass-
forming polymers has been discussed by Hall et al.``` Comparisons were made of the
translational and rotational diusion of small-molecule probes in a polymer near its
glass transition temperature, T
. In the rubbery state, 1.1T
TT
, translational
diusion is much less temperature-dependent than rotational reorientation; in a
quenched glass, translation and rotation have similar temperature dependencies. This
is explained to be a consequence of the fact that in the rubbery state near T
the
breadth of the polymer relaxation distribution is strongly temperature-dependent,
while in the quenched state it is temperature-invariant. Glass transition and ageing in a
model without disorder are presented by Franz and Hertz.``'
The dynamics of intra- and intermolecular motions in biologically active water-
containing biomaterials is considered crucial to their activity. When such biomaterials
are rapidly cooled from ambient to a suciently low temperature, e.g. from :300 to
:100 K, most of the inter- and intramolecular or conformational modes of their
motions become slower and ultimately too slow to be observable at an experimental
timescale of, for example, 10" s. The biomaterial is said to be kinetically frozen, in many
respects in a manner similar to that of vitried liquid.
The A and B forms of NaDNA with a hydration level of between 0.15 and 0.64 (g
water)/(g NaDNA) have been vitried by cooling at rates between 4 and ca.
144 A. Plonka
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2700 Kmin, and their thermal behaviour on reheating was studied from ca. 120 to
300 K by dierential scanning calorimetry (DSC) by Ru disser et al.``` The eects of
the annealing time, t
, for two dierent hydration levels at a xed temperature, and of

the annealing temperature, T
, for a xed t
have been investigated, and the eects of

various T
and t
on the enthalpy and entropy relaxations and recovery were ascer-

tained. From these eects they evaluated t
, the characteristic structural relaxation

time, E*, the activation energy, t
"
, the pre-exponential factor, and [1 as an
empirical parameter for apparent distribution of relaxation times. No DSC features of
signicance that may be attributed to the onset of molecular motions are found for
A-DNA or when the water content is low, but for B-DNA and high water content,
endothermic features resembling the onset of molecular motions, or a glass ;liquid
transition, are observed from ca. 153 K to ca. 263 K. This corresponds to a slower
increase in the heat capacity with temperature than is observed for most glass ;liquid
transitions, and it is attributed to the sum of a large number of relaxation modes of
dierent parts with closely spaced single relaxation times. This is also seen as equival-
ent to a very broad distribution of structural relaxation times or of energy barriers
separating the conformational and other substates corresponding to the various
modes of local motions in a picture of multiple energy barriers. These local modes of
motions involve both DNA segments and the water attached to them. Annealing
vitried B-DNA at temperatures from ca. 153 K to ca. 263 K causes its structures net
energy or enthalpy (and by implication its entropy) to decrease. The magnitude of this
decrease has been measured by using the DSC dierence scans in which the enthalpy
lost on annealing is recovered on reheating, but at a temperature higher than that of
annealing. This recovered enthalpy increases with t
according to the stretched ex-

ponential relation, AH(t
) .1 exp[ (t
/t
)@]. t
seems to remain constant with t
but changes with T
in much the same manner as for synthetic amorphous polymers.

The peak temperature of the endotherm observed during the recovery of the lost
enthalpy, T
, also increases according to a relation, T`
.1 exp[ (t
/t
)@], with the

same values of [ and t
as for the increase in AH(t
). It is concluded that the molecular

segmental motions of B-DNA and of the water attached to it are attributable to a
broad distribution of energy barriers between conformational substates. See also
Sartor and Johari.```
The termphysical ageing, as applied to polymers, encompasses a very wide range of
behaviours, all of which are linked by the same phenomenon, cf. Hutchinson.``" This
phenomenon is the observed change in a property of the polymer as a function of
storage time, at constant temperature, at zero stress, and under no inuence from any
other external conditions. The multitude of properties used for observation has been
the source of the wide range of behaviour, and includes both macrostructural, or bulk,
properties such as specic volume, enthalpy, mechanical and dielectric response, as
well as microstructural or molecular-scale properties which may be probed by, for
example, spectroscopic and scattering techniques. All of these properties have been
reported to exhibit, under appropriate conditions, a behaviour which may be classied
as ageing. In addition, the prex physical is often included in order to distinguish this
phenomenon from those of chemical or biological ageing. Physical ageing involves
only reversible changes in properties, with no permanent modication of the structure,
either chemical or physical, of the material.
The most common situation in which physical ageing is observed is when an
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amorphous polymer is cooled fromabove to belowits glass transition temperature, T
;
the ageing is then manifested as, for example, a reduction in the specic volume or
enthalpy, and an apparent shift of the creep response to longer times. The physical
ageing of polymers has been reviewed by Hutchinson``" in three broad areas: the
changes in bulk thermodynamic properties, namely volume and enthalpy; various
microstructural evidences for structural changes; and changes in mechanical proper-
ties. It was concluded that there is a remarkably good correlation between these
aspects and that they may broadly be linked through the concepts of free volume and
free volume distributions.
A new free volume distribution for amorphous polymers was derived by Chow`'"
on the basis of a lattice model. It provides a good description of the non-Gaussian
spreading observed in positron annihilation experiments for epoxy polymer
resin.`'`'` This new theory shows that the non-Gaussian distribution is a result of
the large density uctuations of holes from their equilibrium. The Gaussian distribu-
tion is recovered in the limit of small uctuations. The size and volume distribution of
the holes is uniquely dened by two structural parameters: the energy of hole forma-
tion and the lattice volume. The theory predicts that increases in temperature will
broaden the distribution and shift its lower peak to higher free volume. Increases in
pressure have the opposite eect. For the evaluation of free volume at glass transition
see Ban et al.`'` and Bartos.`'"
The concepts of free volume and congurational entropy, but particularly the
former,``" have been the basis for a number of phenomenological models of volume
and enthalpy relaxation. Non-linearity, expressed by the equation
t(T, T
'
) t
"
exp
xAh*
RT

(1 x)Ah*
RT
'

(137)
in which the relaxation time t(T, T
'
) depends` in part (x) on the absolute temperature T
and in part (1 x) on the structural temperature T
'
, is a common feature of nearly all
current models of relaxation kinetics. The other feature is to account for the distribu-
tion of relaxation times. This is done by using a stretched exponential, cf. examples of
recent reports on relaxationshipbetween enthalpy relaxation and dynamic mechanical
relaxationof engineering plastics by Yoshida;`'` structural relaxation of glass-forming
polymers based on an equation for congurational entropy by Brunacci et al.,`''
Gomez Ribelles et al.`'``'` and Meseguer Duenas et al.;`'" enthalpy recovery of
poly(ether imide) by Simon;``" physical ageing of poly(ether imide) by Simon et al.;``
enthalpy relaxation in a partially cured epoxy resin by Hutchinson et al.;``` or
physical ageing in poly(vinyl acetate) by Cowie et al.,``` who name the stretched
exponential CowieFerguson equation; and Muzeau et al.``" who introduce indirectly
the stretched exponential. The other way to account for the distribution is to use a
discrete distribution as in the KAHR model.``` For recent remarks on volume
recovery theory see also Struik,``'``` and on the phenomenon of rejuvenation of
physically aged polymers by mechanical deformation see Struik.``` One has also to
note, however, the irreversibility of structural changes induced by stretching in
poly(vinyl chloride) reported by Elicegui et al.``"
The microscopic basis of the glass transition in polymers from neutron scattering
studies were reviewed by Frick and Richter,``" Richter`` and Colmenero and
Arbe.``` For the onset of fast processes in polystyrene and in polypropylene see Frick
146 A. Plonka
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et al.``` and Kanaya et al.,``" respectively. Recent developments in Monte Carlo
simulation of glass transition in polymeric systems were presented by Baschnagel,```
Baschnagel and Fuchs,``' Baschnagel and Binder,``` Binder``` and Rieger.``"
The inuence of the exible alkyl chain spacer on the molecular dynamics of the
glass transition in side-chain liquid-crystalline polymers (SCLCPs) and its dependence
on the spacer length were considered in the framework of the coupling model by Ngai
et al.`"" The idea is that the molecular motions of densely packed systems are
necessarily cooperative in nature because there are dynamical constraints between the
motions of the basic units that arise from their mutual interactions. How these
dynamical constraints should be treated in an irreversible process (i.e. relaxation), in
order to construct the theory that has predictions in agreement with experimental
data, is an open question. The coupling theory is an attempt in this direction. (See also
Ngai and Plazek.`") In this theory, cf. Section 4, dynamical constraints have the eect
of slowing down the averaged relaxation rate of the cooperative motions according to
the time-dependent form of (o
t)L, and n lying within the range 0 On 1 is called the

coupling parameter, which quanties the slowing down of the averaged relaxation rate
of the mutually dynamically constrained motions. The coupling parameter n is a
monotonic increasing function of dynamic constraints. The correlation function of the
relaxation has the Kohlrausch stretched-exponential form, exp[ (t/t*)L]. This is
usually true for segmental motions in many amorphous polymers that are not compli-
cated by the presence of crystallinity, diluent or another miscible polymer, and long
exible side chains which cause internal blending. Short spacer length may enable the
mesogenic groups in the side chain to enhance the degree of cooperativity of the
segmental dynamics responsible for the glass transition, compared with that of the
corresponding parent main-chain polymer without the side chains. However, when the
spacer length becomes long, not only are motions of the mesogenic group and the main
chain decoupled, but also the preponderance of exible methylene chains in the
vicinity of the polymer backbone will diminish the degree of cooperativity of the
segmental dynamics compared with that of the corresponding parent main-chain
polymer without the side chain. The degree of cooperativity is quantied in the
coupling model for SCLCPs by the steepness of the plot of a characteristic relaxation
time, of the segmental relaxation time spectrum against normalized reciprocal tem-
perature, which is operationally dened as the temperature at which is equal to an
arbitrarily chosen but xed time of long duration. Dielectric and mechanical relax-
ation data of several families of SCLCPs published in the past ten years were used to
test this prediction. The results from the analysis of these data are in accord with the
predicted trends. See also Alegria et al.,`"` Perez and Cavaille,`"` and Plazek et al.`""
Bouchaud et al.`"` have analyzed a simple dynamical model of glasses, based on the
idea that each particle is trapped in a local potential well, which itself evolves due to
hopping of neighbouring particles. The glass transition is signalled by the fact that the
equilibrium distribution ceases to be normalizable and dynamics becomes non-sta-
tionary. See also Barrat and Me zard.`"' For measurements thought to provide direct
evidence that the collective character of molecular motion is responsible for the
slowing down of mobility in glasses see Jerome and Commandeur.`"`
Richert`"` has presented evidence for dynamic heterogeneity near T
from the time-

resolved inhomogeneous broadening of optical line shapes. For discussion of multi-
dimensional nuclear magnetic resonance data see Heuer et al.`"", Sillescu'"", and
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Kuebler et al.'" Nanostructure of polymer glasses, log-normal size distribution of
domains, is reported by Mermet et al.'"` from inelastic neutron and Raman scattering
studies of poly(methyl methacrylate). See also Mermet et al.'"` for studies on localized
fast relaxation in poly(methyl methacrylate) glass, Fioretto et al.'"" for studies of
relaxation in poly(methyl methacrylate) and Sauer and Kim'"` for studies on struc-
tural heterogeneity in poly(methyl methacrylate) glasses of dierent tacticity. For an
interpretation of quasielastic neutron scattering and molecular dynamics simulation
results on glass transition in terms of a coupling model see Ngai et al.'"'. For the
independently relaxing nanoscale inhomogeneities as a model for structural relaxation
see Moynihan and Schroeder,'"` Moynihan,'"` and Schroeder et al.'"" Leheny et
al.'" have performed neutron diraction experiments on deuterated propylene glycol,
an organic glass former, at temperatures ranging from where its dynamical response
approaches that of normal liquids to below the point where relaxation times appear to
diverge. Their studies extended over a very broad range of scattering wave vector
(0.01 Q/ 30 ). In contrast to models which predict clustering, they have found
no evidence in the liquid at any temperature for heterogeneities large on molecular
scales. However, they do note subtle changes at shorter lengths. Using molecular
dynamics simulations to model their results, they have identied these changes with
increasing density and increasing orientational order induced by hydrogen bonding in
the liquid as it cools. Analysis of the orientational correlations between molecules
revealed a strong dependence on their relative positions.
In glass-forming polymeric systems the dominating relaxation process is the :
relaxation for which the temperature dependence of the relaxation time shows a
dramatic increase around T
, leading to the glassy state at lower temperatures. This

relaxation is attributed to sequential relaxation of the main chain, and cooperative
relaxation is thought to lead to the glass transition. According to Wagner and
Richert,' for poly(vinyl acetate) no signicant change of the relaxation time distribu-
tion occurs from well above the glass transition at 299.6 K to temperatures below T
,
where the average retardation times attain values up to 10` s. Beside the :-relaxation,
additional relaxations on various faster timescales can be active, which are called
secondary relaxation processes ([-relaxation, -relaxation etc.). Alegria et al.'` have
investigated the eect of the experimental liquidglass transition on the dielectric
relaxation of three amorphous polymers: poly(2-hydroxypropyl ether bisphenol A),
with the repeating unit shown in Scheme 1, poly(vinyl acetate) and poly(vinyl methyl
ether), by means of frequency and time domain dielectric spectroscopies.
They have taken'` as well established that the :-relaxation process in glass-
forming polymers can be well described by means of a Kohlrausch relaxation function.
However, this law gives a description of the relaxation processes which has a closed
expression only in the time domain. In the frequency domain the experimental dielec-
tric results have often been described by the HavriliakNegami (HN)'`'" empirical
relaxation function:
c*(o) c
`
Ac
1
[1 (iot
'`
)?]A
(138)
where c*(o) c'(o) ic"(o) is the complex permittivity, c
`
is its unrelaxed value, Ac is
the relaxation strength, : and are two shape parameters in the range zero to unity
(0 :, 1), and t
'`
is a characteristic relaxation time. Since the HN equation has
148 A. Plonka
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Scheme 1
two independent shape parameters, it is more versatile than the Kohlrausch function
in the sense that the HN equation allows the tting of the experimental behaviour in a
wider variety of systems.'` Furthermore, in eqn. (138) an extra conductivity term,
io
"
o, is usually introduced to account for the contribution of the conductivity to
the dielectric losses.
A comparison between the HN and the Kohlrausch descriptions has recently been
published.'`'' It was shown that, for certain values of : and , the HN relaxation
function is a good representation of the Fourier transformation (FT) of the Kohl-
rausch time decay function u(t). The following empirical correlations among the HN
and Kohlrausch parameters were reported:'`
[ (:)`` (139)
log t log t
'`
2.6(1 [)"`exp( 3[) (140)
The structural state of the glassy polymer was determined by means of dierential
scanning calorimetry. It was found that the relaxation behaviour can be well described
by the Kohlrausch relaxation function above and below T
. The temperature depend-

ence of the characteristic timescale showed clear crossover from a VFT behaviour
toward an Arrhenius behaviour in the liquid-glass transition range. The whole behav-
iour, which extends over 10 decades in timescale, can be fully described by the Adam
and Gibbs theory framework, if a slow change of the congurational entropy in the
glassy state is allowed. On the other hand, when the system falls out of equilibrium [
appears to be slightly higher than the one corresponding to the supercooledliquid. The
behaviour of [ around the glass transition leads the authors to interpret the relaxation
shape as a consequence of a narrow distribution of strongly correlated relaxation
processes.
In subsequent studies, Alegria et al.,'` the inuence of physical ageing on the
dielectric :-relaxation of these amorphous polymers was investigated by means of time
domain dielectric experiments. It was found that the dielectric relaxation behaviour in
a isostructural state out-of-equilibrium can be well described by the Kohlrausch
function, the dielectric relaxation time increasing strongly with ageing time but the
shape parameter being weakly aected by physical ageing. The dependence of the
relaxation time on physical ageing was interpreted in terms of the Adam and Gibbs
theory. The eects of physical ageing on the congurational entropy, obtained by
applying the Adam and Gibbs equation to the dielectric relaxation times, were
compared with the eects on enthalpy relaxation data obtained calorimetrically. For
the three polymers investigated, both quantities equilibrate in the same timescale. A
phenomenological model of physical ageing, with parameters determined from the
equilibrium supercooled melt behaviour, was developed. Assuming that the structural
and dielectric relaxation times are proportional to each other, it was shown that the
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dynamical parameters obtained from equilibrium experiments can account for the
time dependence of both dielectric and enthalpy relaxation in the non-linear regime, at
least at temperatures not too far below the glass transition temperature.
The above method of obtaining the Kohlrausch parameter is quite popular in recent
studies, cf. studies of Floudas et al.'` on dynamics of the strong polymer of n-lauryl
methacrylate below and above the glass transition, studies of Alegria et al.'" on
anomalous dynamical homogeneity of the dielectric :-relaxation in miscible polymer
blends of poly(epichlorohydrin) and poly(vinyl methyl ether), the investigations by
Hofmann et al.'`" of secondary and segmental relaxation in polybutadienes of varying
microstructure, the studies of Sanchis et al.'` on dielectric relaxation in chlorinated
polyethylenepolypropylene copolymers, or the investigations by Arbe et al.'`` of :
and [ relaxations in polybutadiene. For 1 one gets from eqn. (138) the ColeCole
relation, which is related to the stretched exponential. This is the procedure used by,
e.g., Johari and Pascheto'`` in dielectric spectroscopy studies on molecular kinetics
during the growth of the macromolecule poly(di-2-hydroxypropyl ether of bisphenol-
A-n-hexylamine), and by Parthun et al.'`" for comparison of the time-invariant and
time-variant dielectric relaxation data simulated for a macromolecule growth; see also
the discussion by Wasylyshyn et al.'`` of the physics of linear-chain and network
polymerization. One must also note the possibility shown by Garwe et al.'`' in their
studies of the inuence of cooperative :-dynamics on local [-relaxation during the
development of the dynamic glass transition in poly(n-alkyl methacrylates). The
Fourier transform of the HN function for the time domain was numerically calculated
according to
dc
'`
(t)
dt

`
"
Ac
[1 (io/o
"
)?]A
exp(iot)do (141)
and directly tted to the experimental data. Using this method the data measured in
both domains can be analysed by the same model function. Moreover, a combined
evaluation procedure can be used if the determination of the relaxation function
requires data from both the frequency and time domains.
The stretched exponential is used to approximate the time domain results in
numerous other spectroscopic techniques, see e.g. the studies by Diaz-Calleja et al.'``
of the relaxation processes in poly(2-chlorocyclohexyl acrylate) using dielectric relax-
ation and mechanical relaxation spectroscopy; the discussion by Connolly et al.'`` of
viscoelectric and dielectric relaxation behaviour of substituted poly(p-phenylenes); the
discussion by Gomez Ribelles et al.'`" of structural relaxations in poly(methacrylates);
the interpretation by Alegria et al.'`" of TSDC (thermally stimulated depolarization
current) results in the study of the :-relaxation of amorphous polymers; the discussion
by Zanzotto and Stastna'` of dynamic master curves from stretched exponential
relaxation modulus; and the discussion by Bero and Roland'`` of terminal relaxations
in linear and three-arm star polyisoprenes. For a discussion of the orientational
relaxation of dipole particles of dierent sizes embedded in a glassy polymeric matrix
see Patashinski and Ratner.'``
Reaction course
The luminescence emitted by amorphous H
`
O ice at 78 K when irradiated with a
continuous source of 260 nm light has been examined by Quickenden et al.'`" The
150 A. Plonka
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emission spectrum was similar to that from crystalline ice, exhibiting two features
around 340 and 420 nm that had short and long lifetimes, respectively. The rise and fall
times of the 420 nm band were the same within experimental error. Six models, most of
which have been described previously,'`` were tested against the decay curves. Model
1 applies to a rst-order decay where the emission arises from the luminescence of a
species produced directly by the irradiation or by a series of fast processes that
culminates in a rate-determining rst-order step; model 2 assumes that the fall in
luminescence can be described by the sum of two exponential decays, models 3 and 4
assume that the luminescent species is produced by the combinationof two homogene-
ously distributed photolysis products, A and B, with respective equal or unequal
reactant concentrations. Model 5 applies to fractal or tunnelling processes and is
described by the following equation
I Pt@ (142)
where P represents a time-independent constant and [ is a fractional exponent with a
value between 0 and 2. The nal model is that of the author,` written as
I :t
"
(t/t
"
)?exp[ (t/t
"
)?] (143)
where is a pre-exponential factor and t
"
is the eective lifetime.
The equations that give the best t to the entire decay curve, as judged by the lowest
and the most random residuals, were those of a biexponential decay (model 2) and
second-order kinetics with unequal reactant concentrations (model 4). According to
the authors'`" the identical nature of the luminescence rise and decay proles strongly
suggests biexponential kinetics. The 420 nm emission was tentatively attributed to the
"l;X`Htransition of excited OHradicals. Areaction mechanismthat explains the
preceding observations was presented, and the biexponentiality of the 420 nm decay
was attributed to excited OH radicals located in two distinct environments within the
ice lattice. (See also Quickenden et al.'`') The photochemical behaviour of ben-
zophenone in poly(methyl methacrylate) has been studied by Ebdon et al.'`` Charge
transfer processes in polyethylene lm containing two solutes have been studied by
Szadkowska-Nicze et al.;'`` the same authors have investigated'`" the excited state
formation in pulse irradiated polyethylene doped with aromatics. For pulse radiolysis
studies of poly(methyl methacrylate) containing pyrene see Szadkowska-Nicze and
Mayer'"" and for ionic and excited intermediates in pulse irradiated polypropylene
doped with aromatics see Mayer et al.'" Pekcan'"` has reported on uorescence
lifetime distributions in polymer blend-like particles. Krissinel and Mackarchuck'"`
have tried to nd the distance dependence of the electron-transfer rate constant from
the luminescence quenching kinetics in solids assuming that no functional form of this
dependence is known a priori. The existence of a solution and the problem of a set of
solutions are considered. An original numerical procedure of solution is developed.
This procedure needs only a solution of a system of linear equations under non-
negative restrictions. An application of the approach developed to some real lumines-
cence kinetics is presented and an example of interpretation of results is given. The
conclusion is made that the distance dependence of the electron transfer rate constant
has a non-exponential form. The approach presented may be used for the interpreta-
tion of experimental quenching kinetics even if a noticeable anisotropy and structural
eects are expected. Dakhnovskii et al.'"" have described the classical electron transfer
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Scheme 2
in polar glasses by a theory based on a model microscopic Hamiltonian which includes
the discreteness and randomness of the glassy polar modes with distinct orientation.
When congurational dynamics is fast, the reaction is described by exponential
kinetics with a rate constant of non-Arrhenius type. The temperature-dependent rate
constant resembles the tunnelling rate, despite the classical transfer of the electron.
This eect is called false tunnelling. In this limit the possibility of a self-acceleration of
the reaction is pointed out. When congurational dynamics is very slow the reaction
kinetics are non-exponential, with multirelaxation time behaviour. The reaction is
shown to be almost insensitive to temperature change, indicating a possible explana-
tion of a broad temperature-independent range in the rate constant in an electron
transfer in cytochrome-c oxidation. At short times, the reaction accelerates compared
to the exponential behaviour, while at long times it becomes slower. For strongly
exothermic reactions the kinetics are always slower than an exponential decay. A
model of the long-range (2 nm) tunnelling transfer of electrons from donor to
acceptor by mobile charge carriers has been suggested by Kaplan et al.'"`
Kinetics of atomic hydrogen in solid krypton and xenon has been studied by
Eberlein and Creuzburg;'"' the validity of eqn. (15) to describe the thermal bleaching
of hydrogen atoms was presented.
Evaluation methods based on dispersive kinetics were applied by Feldmann et al.'"`
to derive kinetic parameters for the rearrangement of dierently :-substituted nitronic
acids (Scheme 2) generated by ash photolysis (z
'"
347 nm) of o-nitrobenzyl esters.
The rearrangements were performed in polymer matrices of dierent chemical nature:
poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), poly(styrene) (PSt),
and poly(dimethylsiloxane) (PDMS). A non-exponential decay behaviour was ob-
served in rigid and highly viscous matrices. It was analysed in terms of the stretched
exponential and in terms of the model, ascribed to Siebrand and Wildman,'"` which
relates the dispersion to the distribution of energy barriers controlling molecular
motions. It was postulated that the individual decay rate constants are thermally
activated and that the individual energy barrier heights are subject to a Gaussian
distribution around a mean value Ac with a standard deviation o. Hence:
c
R
/c
"
`
`
h(Ac)exp[ v(Ac)t]d(Ac) (144)
Here, v(Ac) v
"
exp[ Ac/RT] is the rate constant of an individual elementary reac-
tion with the activation energy Ac and h(Ac) is the distribution function of the
activation energy. In a polymer matrix Ac is thought to depend on various conforma-
tional parameters which are subject to statistical variations. It seemed reasonable to
the authors to consider the activation energy to be Gaussian:
152 A. Plonka
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Scheme 3
h(Ac)
1
(2o`)`
exp[ (Ac Ac)`/2o`] (145)
Here, o denotes the dispersion factor and Ac the mean activation energy of the
thermally activated decay of the nitronic acid in a polymer matrix. Upon tting the
measured time dependence of c
R
/c
"
to eqn. (144), two independent parameters are
obtained, the dispersion factor o and the average rate constant v given by eqn. (146):
v v
"
exp( Ac/RT) (146)
It was found that the apparent activation energy of the average constant of the
unimolecular reaction is inherent to the nitronic acid and depends only slightly, if at
all, on the chemical nature of the matrix and on the mobility of the matrix. However,
the mobility of the matrix exerts a strong inuence on the dispersion factor o, which is
a measure of the width of the Gaussian distribution of individual energy barrier
heights. With increasing temperature o decreases but approaches zero (transit from
dispersive to non-dispersive, i.e. rst-order kinetics) at temperature denitely higher
than T
. The more pronounced this eect is, the bulkier is the substituent at the
:-position of the nitronic acid. The activation entropy AS
was found to be negative in

all cases, thus substantiating the existence of a formerly postulated cyclic intermediate.
AS
depends only slightly on the chemical nature of the matrix but signicantly
depends on the chemical nature of the nitronic acid: in the case of the unsubstituted
nitronic acid, AS
is much lower than in the cases of the substituted ones. This

dierence is thought to be due to hydrogen bonding, which is only feasible in the case
of the unsubstituted compound.
Richert and Heuer'"" have reanalysed the kinetics of the photochromic rst-order
reaction merocyanine ;spiropyran (Scheme 3) in PMMA. The purpose of the work
was to re-examine kinetic data obtained previously'`" for a photochromically doped
polymer, in which the polymer matrix is believed to impose a distribution of site-
specic activation barriers on the rst-order decoloration isomerization of
merocyanine into the spiropyran form. Because the foregoing coloration process is
UV-driven, it was possible to prepare the equilibrium density and a fast subensemble
as observable educt states by varying the irradiation time. In this manner the photo-
chromic sites are employed for probing the nature of the local polymer environments.
The main issue was to analyse these results in the framework of a formalism similarly
used to dene dynamic homogeneity and heterogeneity based on higher-order time
correlation functions. This latter method turns out to be a general and eective tool for
characterizing the dynamical nature of a relaxation process. As a result, the rst-order
nature of the individual transition was strongly conrmed, although the ensemble-
averaged decay is highly non-exponential and although the site-specic rate constants
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may uctuate. It was noted the possibility of distinctly probing the fast or slowrelaxors
in 4D-NMR experiments`"" which have unambiguously identied heterogeneity of
relaxations in polymers near their glass transition temperature. Similar system has
been discussed by Levitus et al.'` Se et al.'`` have investigated the photochemical
isomerization of azobenzene incorporated in poly(N,N-dimethyl-4-vinyl-
phenethylamine-block-styrene) diblock copolymer by cross-linkage. (See also Shi et
al.'`` for sub-glass-transition motions.)
Oliva et al.'`" have investigated the propagating radicals generated during the
photopolymerization and photo-crosslinking of a trimethacrylate (TMA) and a vinyl-
methacrylate (VMA) monomer. Radical decays were followed at 363423 K. In an
attempt to rationalize the experimental results of radical decay in a quantitative
manner, they have veried that the integrated area of the nine-line ESR patterns
decreases according to a bimolecular process, as expected from the classical termina-
tion mechanism. Linear plots of the reciprocal radical R
concentration vs. time have

been obtained at 423 K for all photopolymerized methacrylates (VMA, TMA and
DMA), while a decrease in slope of these plots (i.e. in rate constant) with increasing
time has been observed at lower temperatures.
The observed decrease in bimolecular rate constant during radical decay kinetics,
which is accompanied by further polymerization and cross-linking, was explained by
considering that radicals are trapped in a solid glassy matrix. They can migrate and
encounter other radicals only through chain propagation or chain transfer, and not
through free diusion, as in gas or liquid phases. The laws of classical kinetics in uid
systems do not apply any longer in these conditions. The authors found that radical
decay results can be satisfactorily interpreted in the light of a dispersive kinetic model.
It was recalled that the dispersive nature of kinetics becomes evident in solids when the
rates of reactions approach those of structural relaxation, and in the limit case the
reaction patterns follow from reaction modelling in statistically disordered systems.
Within this framework, the reaction rate constant k of classical kinetics is replaced by
the time-dependent specic reaction rate k(t) given by eqn. (7). The tting of the
experimental data according to eqn. (32), rewritten as [R
] [R
]
"
(B/:)t? gave
a very good correlation. Values of : increase with temperature, being rather low at
363 K and somewhat higher, but in any case lower than 1, at 393 K, thus conrming
the dispersive nature of radical decay kinetics in this temperature range. In contrast,
: 51 in all cases at 423 K, suggesting that radical decay occurs according to a classical
bimolecular termination mechanism at temperatures above the glass transition of the
polymeric systems (e.g. ca. 413 K for photopolymerized DMA). Values of B are
sensitive to the conversion degree of methacrylate groups which had been reached by
irradiation in each polymeric system, and increase with temperature, as expected.
Radicals R
decay at the fastest rate in photopolymerized VMA, which consequently

should be the system in which polymeric chains maintain the highest mobility. In the
case of radical decay in a photopolymerized mixture of TMAand DMA at 393 K both
parameters, : and B, have intermediate values with respect to those determined for the
two photopolymerized monomers at the same temperature. Dispersive kinetics was
found to be highly adequate for the quantitative interpretation of radical decay results
in glassy polymers, leading to evaluation of parameters which well characterize the
polymeric structure.
The dependence of the dynamic exchange process between two radical conforma-
154 A. Plonka
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tions, R
and R
`
, on temperature further supports the validity of the dispersive

kinetic model applied to the characterization of polymeric structures.'`" The rate of
exchange t
`"
does not increase with temperature according to a simple Arrhenius
plot, as the exchange activation energy increases continuously with increasing tem-
perature. This trend is perfectly compatible with the behaviour expected from the
dispersive kinetic model, which predicts noticeable variations in activation energy
around the transition temperature T
of the polymer. If the temperature is belowT
the
activation energy E approaches the activation energy value E
D
which is expected for
the process under analysis (exchange between two conformations, in the present case).
In polymers E
D
is up to two orders of magnitude lower than the congurational
activation energy E
O
, due to polymer matrix relaxation. On the other hand, at the
high-temperature limit E::E
D
(1 :)E
O
(Section 2), and activation energies are
higher because they include the contribution (1 :) times the activation energy E
O
for
matrix structural relaxation. The experimental results conrmed that the activation
energy of radical conformation exchange in both photopolymerizedTMAand VMAis
very low at relatively low temperatures, while it increases with increasing temperature,
tending to a much higher, constant value. The observed trend conrms that pre-
irradiated VMA should maintain a higher segmental mobility than pre-irradiated
TMA, having a lower T
-value.
Equation (32) was used recently by Janik et al.'`` to describe microradical recom-
bination in pulsed-irradiated aqueous solutions of poly(ethylene oxide), poly(vinyl
alcohol), poly(vinyl pyrrolidone) and poly(acrylic acid). Davydov et al.,'`' restricting
the value of : to 0.5, have used eqn. (32) to describe the kinetics of carbene reactions.
Tolkatchev'`` reviewed dispersive kinetics of some elementary radical reactions in
solids.
Highly reactive species trapped in polymer matrices are made reactive and/or
mobile at the temperature regions of matrix structural relaxations. For those made
reactive in the glass transition region a relationship between decay kinetics and :
segmental dynamics is sought,'`` and the decay kinetics is inuenced by physical
ageing.'`"
Pechukas and Ankerhold''" have analysed the model introduced by Agmon and
Hopeld'' for ligand rebinding kinetics in heme proteins. In the model an activated
process decays to equilibrium with rst-order rate constant k; k depends on a control
variable x which species the particular environment in which the process occurs; x
changes randomly in time, by thermal diusion in a potential U(x). If j(x, 0) is the
initial distribution of x, the diusion-reaction equation for j(x, t) is then
cj(x, t)/ct Dc/ct[cj(x, t)/cx[U'(x)j(x, t)] k(x)j(x, t) (147)
where Dis the diusion constant, [ 1/kT, and U'(x) dU(x)dx. The control variable
x in that case is specifying protein conformation. In the static limit D0, the
distribution attached to each value of x decays separately with its own particular rate
constant k(x)
j(x, t) exp[ k(x)t]j(x, 0) (148)
For single-molecule kinetics see Lu and Xie''` and for the dierences in the chemical
reactivity of individual molecules of an enzyme see Xue and Yeung.''` One imagines
that eqn. (148) is a good approximation also in the slow diusion regime, in which D is
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small. Certainly that is the case if k(x) is bounded below by some non-zero minimum
rate constant and if the initial distribution j(x, 0) is not too widely distorted in shape
from the diusional equilibrium distribution exp[ [U(x)]; in that case, if D is small
the reaction is over before diusion has a chance. More interesting is the case in which
k(x) is arbitrarily small at extreme values of x [say, k(x) ;0 as x;-]. Then no matter
how small D is, at long times some slow-reacting, large-x material remains, disappear-
ing at a rate comparable to the rate of diusion. In this case the static approximation
(148) must fail at long times. In fact, the ultimate long-time decay of j(x, 0) is perfectly
well understood, even in this case, courtesy of the familiar trick that converts eqn. (147)
into a Schro dinger-type dierential equation: it is a single-exponential decay with a
rate constant determined by the lowest eigenvalue of the Schro dinger-type operator,
and in this operator the kinetic energy term is proportional to D.
At short times the decay is well described by the static approximation (148), in which
D does not gure and the entire spectrum of rate constants k(x) is important; at long
times the decay is well described by a single exponential, with the exponent determined
by competition between D and the low-k tail of the function k(x). The purpose of
Pechukas and Ankerhold''" was to describe the transition from short-time to long-
time decay. What happens is easy to describe in words. For simplicity, suppose that the
initial distribution is in diusional equilibrium, j(x, 0), and that k(x) is a monotonically
decreasing function of x. As time goes on, the reaction preferentially eats away the left
side of the distribution, where k is larger; the distribution moves to the right and
narrows. Diusion attempts to restore equilibrium by pushing the distribution to the
left and broadening it, but if D is small the eect is weak, and the reaction dominates
until the distribution is far to the right and very narrow, so far out of diusional
equilibrium and so far into the low-k region that diusion and reaction compete on
equal footing. The shape of the distribution then does not change, only its magnitude
declines: this is the long-time single-exponential limit. The shape of the distribution is
now very distorted from diusional equilibrium, so the relevant diusion rate is not
simply O(D), but something larger; likewise, the ultimate reaction rate (when diusion
and reaction balance) is not simply O(D) but something larger; and one may anticipate
that the time of transition, fromstatic decay [eqn. (148)] to single exponential decay, is
not simply O(D) but something shorter. This picture has been conrmed by the
calculations.
These results have to be compared with those of Agmon et al.''" and Berlin et al.,''`
who have discussed a transition from multiexponential to single-exponential decay
under conditions that were essentially the opposite of the conditions assumed by
Pechukas and Ankerhold.''" The initial x distribution was a nonequilibrium one; D
was so large that the distribution then relaxed to equilibrium by diusion alone
without signicant distortion by the rate constant function k(x). For further develop-
ments of the model see Berlin et al.,"` Basilevsky and Davidovitch,''' Berlin''` and
Berlin and Burin.''`
For a protein mechanism model of enzymatic reactions see Kurzynski,''" for a
statistical model of chemical reactions involving proteins see Kurzynski.'`"
The Staebler-Wronski eect,'` i.e. the decay of photoconductivity upon prolonged
illumination, is a major limitation for applications of hydrogenated amorphous silicon
(:-Si: H) and related materials in photoelectric devices such as solar cells. Attention is
focused on the decay of photoconductivity or lifetime and the generation of defects as
156 A. Plonka
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recombination centres. The photoconductivity, electron lifetime and electron drift
mobility in intrinsic hydrogenated amorphous silicon (:-Si: H) and hydrogenated
amorphous silicon carbide (:-SiC: H) while light soaking were determined by Tang
and Braunstein'`` with the use of a photomixing technique. In addition to the decay of
the photoconductivity and electron lifetime, continuous decay of the electron drift
mobility was found during the light soaking process, which reveals that the light-
induced metastable defects of the StaeblerWronski eect results in scattering as well
as recombination of charge carriers. The drift mobility decreased by a factor of 2 for 20
light soaking at 2.5 sun intensity. Experimental data were tted to a stretched ex-
ponential law. Dierent stretched-exponential parameters for photoconductivity, life-
time and drift mobility were obtained, which indicates the production of defects with
dierent generation kinetics upon light soaking. For anomalous charge screening in
the radiation-induced recombination of charged defects in ionic solids see Kuzov-
kov.'`` Thermally assisted tunnelling of BH complex in silicon has been discussed by
Noya et al.'`"
The eects of illumination on the dispersive diusion of hydrogen in :-Si: H were
studied by Greim et al.'``'`' For energy-level dynamics of deep gap states in hydro-
genated amorphous silicon under illumination see Arkhipov and Adriaenssens,'`` for
temperature-dependent distribution of activation energies in amorphous semiconduc-
tors see Arkhipov et al.,'`` and for generalized defect annihilation kinetics for struc-
tural relaxation in amorphous silicon see Shin and Atwater.'`" Kinetics and dynamics
of hydrogen adsorption and desorption on silicon surfaces was reviewed recently by
Doren.'`" For level statistics for electronic states in disordered fractal see Katomeris
and Evangelou.'`
6 Heterogeneous systems
According to Avnir et al.'`` chemical reactions were traditionally treated in terms of
three major parameters: the nature of the chemical bond which is formed between the
reacting molecules; the stereochemical requirements or restrictions which govern this
molecular association; and the energetic prole of the reaction. Heterogeneous chemis-
try introduced a fourth parameter: the structure and geometry of the environment in
which the reaction takes place. The geometry parameter is as important as the three
other parameters, to the extent that it alone can dictate whether a reaction will take
place at all. The geometry problem in chemistry had been in the past unapproachable.
This has been changed for good. Fractal geometry has provided the proper language
and the necessary vocabulary to reformulate some classical problems in heterogeneous
chemistry, and the crucial importance for scientic progress of being able to do so
cannot be underestimated. The origin of fractals is a dynamical, not a geometrical,
problem.'`` For the thermodynamics of fractals (revisited with wavelength trans-
forms, introduced as a mathematical tool in signal analysis in the early eighties), see
Arneodo et al.'`" The examples collected by Avnir et al.'`` seem to indicate that the
promises of fractal geometry have, at least in part, been fullled. These examples have
to be supplemented by the studies of Makse and Amaral'`` and Amaral et al.'`' on
scaling properties of driven interfaces in disordered media; a multifractal scaling
analysis presented by Lee and Lee;'`` Makses'`` discussion on singularities and
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avalanches in interface growth with quenched disorder; Gadomskis'`" stochastic
approach to the evolution of some polycrystalline (bio)polymeric complex systems;
fractal surface analysis by using adsorption data presented by Sze and Lee,'"" Sahouli
et al.'" and Blacher et al.;'"` the use of fractals and kinetic equations to model
thermally induced hillock formation and growth in thin metal lms presented by
Chaiken and Goodisman;'"` Jansens'"" Monte Carlo simulations of chemical reac-
tion on a surface with time-dependent reaction rate coecient; the discussion by
Goodman et al.'"` on trigger waves in a model for catalysis; studies by Khrustova et
al.'"' on delay-induced chaos in catalytic surface reactions; and ion transport in
porous Sn oxide lms interpreted by Isidorsson et al.'"` in terms of a fractal dimension
of a surface relief. See also Zhdanov and Kasemo'"` for kinetics of rapid heterogen-
eous reactions on the nanometre scale.
Bychuk and OShaughnessy'""
`"` have discussed the anomalous diusion on

liquidliquid and liquidsolid interfaces. The general problem of surface diusitivities
and reaction rate constant was presented by Allen and Seebauer.`"` Hyperdiusion
from rough surfaces was reported by Vandembroucq et al.`"" Vattulainen et al.`"`
have studied the non-Arrhenius behaviour of surface diusion near the second-order
phase transition boundary of an adsorbate layer. In contrast to expectation based on
macroscopic thermodynamic eects, they have shown that this behaviour can be
related to the average microscopic jump rate, which in turn is determined by the
waiting-time distribution W(t) of single-particle jumps at short times. At long times,
W(t) yields a barrier that corresponds to the rate-limiting step in diusion. The
microscopic information in W(t) should be accessible by scanning microscopy
measurements. Garcia-Ayuso et al.`"' reported on the eect of surface fractality on the
permeability of transparent gas barrier coatings. Ionic wave propagation through
biomembrane channels has been discussed by Gadomski.`"`
Verdi and Miotello`"` have proposed a model for the silicon oxidation process in a
dry atmosphere, where the growing oxide is seen not as a continuous random lattice
but, instead, as a granular random lattice through which oxygen diusion occurs. A
reactive layer connects the oxide with the Si bulk at the SiO
`
/Si interface. The model
was applied to a representative set of experimental results, obtained at dierent
temperatures and oxygen pressures, leading to a consistent picture of the oxidation
process in terms of a fractal geometry with a denite correlation 54 nm, and
random-walk dimension d
`
53.25. The same idea was used by Verdi and Miotello for
hydrogen dimerization as a probe for investigation of :-SiO
`
structure,`"" and for
analysis of the transport properties of hydrogen and oxygen in non-crystalline SiO
`
,
Verdi and Miotello.`"
Kinetics of intersystem electron transfer within triplet radial ion pairs on silica was
studied by Levin et al.` All transient decays were well tted either to the dispersed
kinetic model of Albery et al.`` or to stretched exponential decay, with similar
goodness of t. Both functions provided an adequate description of the fast compo-
nents of transient kinetic curves using only two parameters. In the Albery model of
Gaussian distribution analysis of rst-order rate constants, the absorption is given by
AJ
R
/AJ
"
`(1
>`
`
exp( x`)exp[ k
texp(x)]dx
(149)
where AJ
"
is the initial change in light reection after the laser pulse, k
is the average
158 A. Plonka
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rst-order rate constant, is the width of the distribution, and
characterizes the
contribution of the slow component.
The stretched exponential function, which contains the same amount of parameters
as function (149) and which is able to give the same good t to experimental kinetic
curves in the study, was written as
AJ
R
/AJ
"
(1
D
)exp[ (k
D
t)D ]
D
(150)
It was stressed that relation (150) is derived from the fractal-like behaviour with a
time-dependent rst-order rate constant k(t) k'
D
tF fkD
D
tD. In terms of fractal
models the heterogeneity constant, h, is a parameter theoretically related to the
spectral fractal dimension of the reaction domain, ranging between 0 (for classical
homogeneous kinetics) and 1.
For a relationship between the heterogeneity constant h and the dispersion par-
ameter see the previous review.` Here we note that
: 1 h (151)
In a classic paper entitled Can one hear the shape of a drum? Kac`` considered a
problem which, in the context of a classic problem related to diusion in restricted
geometries considered by Hu rlimann et al.,`" is equivalent to determining the struc-
ture of the poregrain interface from the spectral function of the diusion equation.
Recently there has been much interest in Kacs problem in connection with studies of
quantum chaos.`` Hu rlimann et al.`" were concerned with the experimental and
theoretical analysis of the spectral function
G(t) Y
`
_
L
exp( z
L
t) (152)
where z
L
are the eigenvalues of the diusion equation, which are, of course, deter-
mined by the geometry of the pore space. Kac`` studied the early time asymptotics of
G(t) and showed that this function contains important information about the structure
of the poregrain interface. More particularly, Kac posed the following problem: if all
the eigenvalues, z
L
, of two dierent drums (which obey the same eigenvalue equation
and the same boundary conditions) are identical, must the two drums be congruent in
the sense of Euclidean geometry? After 25 years of struggle, mathematicians have
recently succeeded in answering this question`' and have shown that it is possible to
construct dierent drums which produce identical spectra. They showed, further, that
a non-isometric transformation connects the pairs of eigenfunctions belonging to each
eigenvalue. Recently Sridhar and Kudrolli`` have given a vivid experimental demon-
stration of this theorem. Despite that it was possible for Hu rlimann et al.```" to
determine the ratio of the surface area to the pore volume fromshort-time asymptotics.
Extraction of the energy distribution functions of heterogeneous surfaces from their
desorption kinetics is discussed by Cerofolini and Re.``"
Closely connected is the challenging problemof studying the scattering of light from
fractal surfaces, especially the WeylBerry conjecture that the high frequencies of
such fractal drums are governed by the Hausdor (fractal) dimension of their bound-
ary. For rigorous mathematical treatment of the problem see e.g. Lapidus,``
``"
Kigami and Lapidus``` and Lapidus and Maier.``'
Agglomerations of matter which fall into the size range of clusters and ultrane
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particles play a prominent role in nature and technology. Chaiken and Goodisman```
have described a rigorous connection between a coalescence growth model employing
the Smoluchowski equation and the log-normal distribution which has been used for
decades to classify empirically small particle distributions. The model assumes that
only binary collisional events occur, there is conservation of monomers over the
lifetime of the process, the clusters can be represented using a mass fractal approach
and there are no magic numbers. Numerically, it is easy to account for the eects of
evaporation, magic numbers, other inhomogeneities and possibly a non-conservative
process. The model correctly incorporates the existence of multiple kinetic pathways
for producing almost all cluster sizes. The properties of elemental cluster size distribu-
tions can apparently be related to the nature of the monomers as represented by the
Periodic Table. The model classied cluster size distributions on the basis of a single
scaling parameter which itself is a function of the dimensionality of the space in which
the coalescence process occurs, the fractal dimensionality of the clusters, the fractal
dimensionality of the trajectories of the agglomerating species between collisions, and
the scaling of the cluster velocities with increasing cluster size. See also Chaiken and
Goodisman.`````" Structure and arrangement of clusters in cluster aggregation were
discussed by Haw et al.;``" the relationship between fractals and clusters and order-
statistics was developed by Lavenda.`` Wattis and Coveney``` have presented a
model which includes the catalytic eects of clusters on the rate of formation of other
clusters. An application to cement hydration is shown. Diusion of clusters with
randomly growing masses has been discussed by Luczka et al.``` The inuence of
solutesolute interactions on segregation processes in multi-component solid sol-
utions, leading to the formation of a new phase with a given stoichiometric composi-
tion, has been investigated by Slezov et al.``" Expressions for the nucleation and
growth rates have been derived. Estimates were developed for the time required to
establish a steady-state nucleation rate in the system and the time interval for which
such a steady-state can be sustained. Based on these results, it is anticipated that a
method for an experimental determination of the parameters describing the interac-
tion of the solute components could be developed. The kinetic equation describing the
evolution of the cluster size distribution function has been generalized to account for
stochastic eects due to both uctuations in the growth rate and possible spatial
correlations of the evolving clusters in the matrix. The possible inuence of such
stochastic eects (thermal noise and random coalescence) on coarsening, described by
such additional terms, has been discussed. For a critical discussion of the analytical
approach to the normal grain growth of materials in a d-dimensional space with some
possible extensions to other growth phenomena see Gadomski.```
Miyake et al.``' have studied the inverse isotope eects in the surface diusion of
atoms. Diusion of atomic hydrogen on the surface and in the bulk of metals was seen
as a stimulating problem not only from a practical point of view but also as a
fundamental problem of quantum mechanics, since a signicant quantum eect is
expected for the lightest element. At high temperature, diusion occurs classically by
thermal activation following the Arrhenius equation. When the temperature decreases
down to around 100 K on metal surfaces one observes a classical quantum crossover
into a tunnelling region where the hopping rate shows a less pronounced temperature
dependence. The classicalquantumcrossover has been precisely investigated theoreti-
cally with a path integral formulation, which is one of the most powerful techniques to
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give a unifying description of hopping in both classical and quantum regions. Path
integral formulation leads to the well known fact that the crossover occurs distinctly in
a narrow temperature region. In this formulation, the crossover temperature is de-
nitely characterized by deformation of a Feynmann path mainly contributing to the
hopping, i.e. emergence of an instanton path describing tunnelling (cf. Section 2).
In the case of hydrogen diusion one can utilize three isotopes of hydrogen to
observe an interesting eect in the vicinity of the crossover temperature arising from
the dierence in mass of the hopping particles. Usually, an isotope eect is seen so that
lighter particles diuse more easily. It has been reported, however, that hydrogen
diusion on W(110) shows an anomalous isotope eect in that the heavier particle
diuses faster just above the classicalquantumcrossover.```
``" This inversion of the

mass dependence of the diusion constant is called the inverse isotope eect. The same
eect is also observed in the bulk diusion below a certain temperature (ca. 800 K for
Pd).`""
The inverse isotope eect is peculiar for the following reason.``' When we consider
the diusion from a microscopic view, an elementary process is thought to be the
hopping of a particle (hydrogen) from a stable site to a neighbouring site. At high
temperature the particle hops classically over the potential barrier. Since the potential
is the same for any isotope, mass dependence comes only from the attempt frequency,
which leads to the hopping rate, I, being proportional to m`. At low temperature
where the particle tunnels quantum mechanically, I is expected to increase exponen-
tially with decreasing m; this is easily derived from WKB approximation. Naively, we
expect that at around the crossover temperature the mass dependence of I will be
intermediate between the high temperature m` dependence and the low-tempera-
ture exponential behaviour. Thus the inverse isotope eect is unlikely to exist at any
temperature.
However, as a result of numerical simulations using the quantum transition state
theory, which is based on path integral formulation, Rick et al.`" found the inverse
isotope eect for the hydrogen diusion from a Pd(111) surface into the subsurface
layer in the intermediate temperature region. They interpreted it as follows. When the
particle reaches the top of the potential barrier, it is highly conned spatially in the
directions orthogonal to the diusion path due to the surrounding metal atoms, and
will have a much larger zero-point energy than it will in the well bottoms, which
suppresses the hopping. This connement eect has a larger inuence on lighter
particles, so that the inverse isotope eect could be induced. (See also Mattsson and
Wahnstro m.`"`)
Miyake et al.``' have claried by quantum Monte Carlo simulation that a decrease
in the hopping rate by connement, competing with an increase by tunnelling, indeed
induces the inverse isotope eect within a certain temperature range above a classical-
quantum crossover temperature. Furthermore, at high temperatures, the connement
eect can be induced in the potential barrier for diusion and the inverse isotope eect
can be described with a reduced one-dimensional model within Feynmans variational
method. For hydrogen and deuterium diusion in titanium dihydrides/dideuterides
see Kaess et al.;`"` for hopping and tunnelling of hydrogen and deuteriumin semicon-
ductors see Cannelli et al.`"" Grela and Colussi`"` have studied the kinetics of
stochastic charge transfer and recombination events in semiconductor colloids.
The nature of the surface of ice is of critical importance to several areas of science,
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including atmospheric and interstellar chemistry and meteorology. Despite many
years of ice research, the knowledge of the molecular structure of the ice surface is
much more limited than that of the ice interior. So it is worth noting the recently
developed experimental technique of preparing stable deposits of ice nanocrystals of
very large surface area; the deposits proved to be useful in spectroscopic investigations
of ice surface properties and of iceadsorbate interactions.`"'
`"`
Ball and Davies`"" have analysed the gating mechanism of a single ion channel
which is usually modelled by a continuous-time Markov chain with a nite state space.
The state space is partitioned into two classes, termed open and closed, and it is
possible to observe only which class the process is in. In many experiments channel
openings occur in bursts. This can be modelled by partitioning the closed states further
into short-lived and long-lived closed states, and dening a burst of openings to be a
succession of open sojourns separated by closed sojourns that are entirely within the
short-lived closed states. There is also evidence that bursts of openings are themselves
grouped together into clusters. This clustering of bursts can be described by the ratio of
the variance Var[N(t)] to the mean N(t), of the number of bursts of openings
commencing in (0, t]. Two methods of determining Var[N(t)]/E[N(t)] and
lim
R
`
Var[N(t)]/E[N(t)] were developed, the rst via an embedded Markov renewal
process and the second via an augmented continuous-time Markov chain. The theory
was illustrated by a numerical study of a molecular stochastic model of the nicotinic
acetylcholine receptor. Extensions to semi-Markov models of ion channel gating and
the incorporation of time interval omission were discussed. Eizenberg and Klafter``"
have investigated the motion of molecules in a time-dependent environment that
involves crossing of several geometrical barriers that act as bottlenecks. The work has
been motivated by the multibarrier nature of ligand motion in protein. They have
solved explicitly the cases of two bottlenecks and two correlated uctuating bottle-
necks.``"
For non-linear theory of ionic transport through track-etched nuclear membranes
see Grzywna et al.`` These membranes have been present in membrane science for
more than three decades in both basic research, in which they have been used as
prototypes of porous membranes separating two electrolyte solutions, and in technol-
ogy, being used in various devices mostly from the ltration family.
7 Concluding remarks
The research on dispersive rate processes in condensed media continues to expand in
its scientic scope. Its impact on scientic activity in numerous areas of study,
including some branches of mathematics, cannot be overestimated. In the nineties, the
tightening of links between experiments, theory and computer simulations is evidently
rewarded.
The promises of dispersive kinetics have been fullled in a substantial part. Reaction
patterns with a time-dependent specic reaction rate, once introduced in a heuristic
manner, are now well rationalized by stochastic models of reactions in disordered
and/or low-dimensional media. The variability of dispersive reaction patterns, needed
to reproduce the experimental results adequately, is seen to arise froma coupling of the
reaction course to the stochastic behaviour of the reactant environment.
162 A. Plonka
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In the limit of ecient renewing of reactant environment classical kinetic patterns
with a constant specic reaction rate are recovered. It is possible to extend the
traditional interpretation of the constant specic reaction rate in terms of an energy
prole along the reaction path to a time-dependent specic reaction rate and a
time-dependent activation energy. New perspectives are, however, seen, as the once
abstract notions of fractal space and time, used in stochastic models of dispersive
kinetics, now appear naturally and inevitably in chaotic dynamics.
Acknowledgements
I thank Professor Graham Webb for his suggestion that I write this review and to my
wife Ewa for her invaluable help in all work and for the nal formof the text. This work
was supported by the Polish State Scientic Research Committee (KBN), in part by
Grant 3 T09A 025 10.
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Dispersive Kinetics

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Dispersive Kinetics

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job:L0434J 9-7-1998 page:1 colour:0

. At the end of the interval the moments lK(t), of the survival

' to evaluate f (k) numerically, in addition to a representation of f(k) in

] 0. Also, independently of the numerical value of : one has, cf. eqn.

. This is true despite t, - from eqn. (32), and one might be

, etc. In numerous cases, es-

the apparent activation energy. If the

are, respectively, the entropy and the enthalpy of activation. The

. If the compensation behaviour is observed, the

, is the slope of the plot of AH

with increasing temperature) and it is characterized by a compensation point. It was

, also called the isokinetic tem-

. On the other hand,

was related to the breadth of the glass

w(r r')p(r', t')dt' (60)

z(r r')p(r', t')dt' (61)

`` These analogies have

for a solid, and zero for a uid, J

for a solid or the steady-state recoverable

"` Huber,"'"` and Sciortino and Tar-

, which denotes the onset of the

the chain behaves as a Rouse chain

`` and layers`` as well as hole transport in

``` and in vapour deposited molecular glasses``'

`" For a low-temperature approximation

. Within A there is always an area A

consisting of particles that leave A within a limited time period t

. If the particles performing a nite motion never return

are equal, which

begins to retard the

, Arrhenius temperature dependencies

, for the :-relaxation in liquid and crystalline

; evidence for the latter two is presented. For a hierarchically

``` on the surface reaction model

"`` who aimed to provide a general expression for a rate constant

is the thermal equilibrium rate constant of the usual theories, such as

is the free energy of activation and v is the frequency factor at temperature

was shown to exhibit a surprising degree of universality associated

scales with molecular weight

:1/ln N, and above the threshold, k

``` The term glass transition has become generalized to cover

depends on temperature according to the VFT eqn. (48). (3) Many

and the presence of excitations in the mesoscopic frequency range 101000GHz

. For evidence of two structural relaxation processes

. In the rubbery state, 1.1T

, for two dierent hydration levels at a xed temperature, and of

have been investigated, and the eects of

on the enthalpy and entropy relaxations and recovery were ascer-

, the characteristic structural relaxation

according to the stretched ex-

seems to remain constant with t

but changes with T

in much the same manner as for synthetic amorphous polymers.

, also increases according to a relation, T`

)@], with the

as for the increase in AH(t

). It is concluded that the molecular

t)L, and n lying within the range 0 On 1 is called the

from the time-

, leading to the glassy state at lower temperatures. This

. The temperature depend-

was found to be negative in

is much lower than in the cases of the substituted ones. This