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Energy redistribution in reacting systems
Roberto Marquardt and Martin Quack
A3.13.1 Introduction
Energy redistribution is the key primary process in chemical reaction systems, as well as in reaction systems
quite generally (for instance, nuclear reactions). This is because many reactions can be separated into two
steps:
(a) activation of the reacting species R, generating an energized species R :
R R
(A3.13.1)
(A3.13.2)
The first step (A3.13.1) is a general process of energy redistribution, whereas the second step (A3.13.2)
is the genuine reaction step, occurring with a specific rate constant at energy E. This abstract reaction
scheme can take a variety of forms in practice, because both steps may follow a variety of quite different
mechanisms. For instance, the reaction step could be a barrier crossing of a particle, a tunnelling process or
a nonadiabatic crossing between different potential hypersurfaces to name just a few important examples in
chemical reactions.
The first step, which is the topic of the present chapter, can again follow a variety of different mechanisms.
For instance, the energy transfer could happen within a molecule, say from one initially excited chemical
bond to another, or it could involve radiative transfer. Finally, the energy transfer could involve a collisional
transfer of energy between different atoms or molecules. All these processes have been recognized to be
important for a very long time. The basic idea of collisional energization as a necessary primary step in
chemical reactions can be found in the early work of vant Hoff [1] and Arrhenius [2, 3], leading to the famous
Arrhenius equation for thermal chemical reactions (see also chapter A3.4)
k(T ) = A(T ) exp
EA (T )
.
RT
(A3.13.3)
This equation results from the assumption that the actual reaction step in thermal reaction systems can happen
only in molecules (or collision pairs) with an energy exceeding some threshold energy E0 which is close, in
general, to the Arrhenius activation energy defined by equation (A3.13.3). Radiative energization is at the basis
of classical photochemistry (see e.g. [47] and chapter B2.5) and historically has had an interesting sideline in
the radiation theory of unimolecular reactions [8], which was later superseded by the collisional Lindemann
mechanism [9]. Recently, radiative energy redistribution has received new impetus through coherent and
incoherent multiphoton excitation [10].
In this chapter we shall first outline the basic concepts of the various mechanisms for energy redistribution,
followed by a very brief overview of collisional intermolecular energy transfer in chemical reaction systems.
The main part of this chapter deals with true intramolecular energy transfer in polyatomic molecules, which
is a topic of particular current importance. Stress is placed on basic ideas and concepts. It is not the aim of
this chapter to review in detail the vast literature on this topic; we refer to some of the key reviews and books
[1132] and the literature cited therein. These cover a variety of aspects of the topic and further, more detailed
references will be given throughout this review. We should mention here the energy transfer processes, which
are of fundamental importance but are beyond the scope of this review, such as electronic energy transfer by
mechanisms of the Forster type [33, 34] and related processes.
A3.13.2 Basic concepts for inter- and intramolecular energy transfer
The processes summarized by equation (A3.13.1) can follow quite different mechanisms and it is useful to
classify them and introduce the appropriate nomenclature as well as the basic equations.
A3.13.2.1
(a) The first mechanism concerns bimolecular, collisional energy transfer between two molecules or
atoms and molecules. We may describe such a mechanism by
M + R M + R
(A3.13.4)
or more precisely by defining quantum energy levels for both colliding species, e.g.
{M(EMi ) + R(ERi )}I {M(EMf ) + R(ERf )}F .
(A3.13.5)
This is clearly a process of intermolecular energy transfer, as energy is transferred between two molecular
species. Generally one may, following chapter A.3.4.5, combine the quantum labels of M and R into one
level index (I for initial and F for final) and define a cross section FI for this energy transfer. The specific
rate constant kFI (Et,I ) for the energy transfer with the collision energy Et,I is given by:
kFI (Et,I ) = FI (Et,I )
with the reduced mass:
=
1
1
+
mM mR
2Et,I
(A3.13.6)
(A3.13.7)
(A3.13.8)
Some of the internal (rovibronic) energy of the atomic and molecular collision partners is transformed into
extra translational energy Et = Et,F Et,I (or consumed, if Et is negative). If one averages over a thermal
distribution of translational collision energies, one obtains the thermal rate constant for collisional energy
transfer:
8kB T 1/2
kFI (T ) =
x exp(x)FI (kB T x) dx.
(A3.13.9)
We note here that the quantum levels denoted by the capital indices I and F may contain numerous energy
eigenstates, i.e. are highly degenerate, and refer to chapter A3.4 for a more detailed discussion of these
equations. The integration variable in equation (A3.13.9) is x = Et,I /kB T .
(b) The second mechanism, which is sometimes distinguished from the first although it is similar in kind,
is obtained when we assume that the colliding species M does not change its internal quantum state. This
special case is frequently realized if M is an inert gas atom in its electronic ground state, as the energies needed
to generate excited states of M would then greatly exceed the energies available in ordinary reaction systems
at modest temperatures. This type of mechanism is frequently called collision induced intramolecular energy
transfer, as internal energy changes occur only within the molecule R. One must note that in general there
is transfer of energy between intermolecular translation and intramolecular rotation and vibration in such a
process, and thus the nomenclature intramolecular is somewhat unfortunate. It is, however, widely used,
which is the reason for mentioning it here. In the following, we shall not make use of this nomenclature and
shall summarize mechanisms (a) and (b) as one class of bimolecular, intermolecular process. We may also
note that, for mechanism (b) one can define a cross section fi and rate constant kfi between individual, nondegenerate quantum states i and f and obtain special equations analogous to equations (A3.13.5)(A3.13.3),
which we shall not repeat in detail. Indeed, one may then have cross sections and rates between different
individual quantum states i and f of the same energy and thus no transfer of energy to translation. In this
very special case, the redistribution of energy would indeed be entirely intramolecular within R.
(c) The third mechanism would be transfer of energy between molecules and the radiation field. These
processes involve absorption, emission or Raman scattering of radiation and are summarized, in the simplest
case with one or two photons, in equations (A3.13.10)-(A3.13.12):
Ri + h Rf
Ri Rf + h
Ri + hi Rf + hf
(absorption)
(emission)
(A3.13.10)
(A3.13.11)
(Raman scattering).
(A3.13.12)
In the case of polarized, but otherwise incoherent statistical radiation, one finds a rate constant for radiative
energy transfer between initial molecular quantum states i and final states f:
kfi =
8 3 Iz
|M z |2
h2 (4 0 )c fi
(A3.13.13)
where Iz = dI z /d is the intensity per frequency bandwidth of radiation and Mfiz is the electric dipole
transition moment in the direction of polarization. For unpolarized random spatial radiation of density ()
per volume and frequency, Iz /c must be replaced by ()/3, because of random orientation, and the rate of
induced transitions (absorption or emission) becomes:
kfiinduced = Bfi ()
(A3.13.14)
8
()|Mfi |2 .
3h2 (4 0 )
Bfi is the Einstein coefficient for induced emission or absorption, which is approximately related to the absolute
value of the dipole transition moment |Mfi |, to the integrated cross section Gfi for the transition and to the
Einstein coefficient Afi for spontaneous emission [10]:
Bfi =
c
c3
Gfi =
Afi
h
8 hfi3
(A3.13.15)
with
fi () 1 d
Gfi =
line
(A3.13.16)
Figure A3.13.1. Schematic energy level diagram and relationship between intermolecular (collisional or radiative) and
intramolecular energy transfer between states of isolated molecules. The fat horizontal bars indicate thin energy shells of
nearly degenerate states.
and fi () the frequency dependent absorption cross section. In equation (A3.13.15), fi = |Ef Ei |/ h.
Equation (A3.13.17) is a simple, useful formula relating the integrated cross section and the electric dipole
transition moment as dimensionless quantities, in the electric dipole approximation [10, 100]:
Gfi
Mfi 2
41.624
.
Debye
pm2
(A3.13.17)
From these equations one also finds the rate coefficient matrix for thermal radiative transitions including
absorption, induced and spontaneous emission in a thermal radiation field following Plancks law [35]:
kfi = Afi
sign (Ef Ei )
.
exp((Ef Ei )/kB T )) 1
Finally, if one has a condition with incoherent radiation of a small band width
absorption band with ( ) (), one finds:
kfiinduced =
()
I
h
(A3.13.18)
exciting a broad
(A3.13.19)
where I is the radiation intensity. For a detailed discussion refer to [10]. The problem of coherent radiative
excitation is considered in sections A3.13.4 and A3.13.5 in relation to intramolecular vibrational energy
redistribution.
(d) The fourth mechanism is purely intramolecular energy redistribution. It is addressed in the next
section.
A3.13.2.2
Purely intramolecular energy transfer occurs when energy migrates within an isolated molecule from one
part to another or from one type of motion to the other. Processes of this type include the vast field of
molecular electronic radiationless transitions which emerged in the late 1960s [36], but more generally any
type of intramolecular motion such as intramolecular vibrational energy redistribution (IVR) or intramolecular
vibrationalrotational energy redistribution (IVRR) and related processes [3739]. These processes will be
discussed in section A3.13.5 in some detail in terms of their full quantum dynamics. However, in certain
situations a statistical description with rate equations for such processes can be appropriate [38].
Figure A3.13.1 illustrates our general understanding of intramolecular energy redistribution in isolated
molecules and shows how these processes are related to intermolecular processes, which may follow any of
the mechanisms discussed in the previous section. The horizontal bars represent levels of nearly degenerate
states of an isolated molecule.
Having introduced the basic concepts and equations for various energy redistribution processes, we will
now discuss some of them in more detail.
A3.13.3 Collisional energy redistribution processes
A3.13.3.1
The fundamental kinetic master equations for collisional energy redistribution follow the rules of the kinetic equations for all elementary reactions. Indeed an energy transfer process by inelastic collision, equation (A3.13.5), can be considered as a somewhat special reaction. The kinetic differential equations for
these processes have been discussed in the general context of chapter A3.4 on gas kinetics. We discuss here
some special aspects related to collisional energy transfer in reactive systems. The general master equation
for relaxation and reaction is of the type [1113, 15, 25, 40, 41]:
dcj (t)
= F ({ck (t)})
dt
cj (t = 0) = cj 0 .
(A3.13.20)
(A3.13.21)
The index j can label quantum states of the same or different chemical species. Equation (A3.13.20) corresponds to a generally stiff initial value problem [42, 43]. In matrix notation one may write:
dc(t)
= F [c(t)]
dt
c(t = 0) = c0 .
(A3.13.22)
(A3.13.23)
There is no general, simple solution to this set of coupled differential equations, and thus one will usually
have to resort to numerical techniques [42, 43] (see also chapter A3.4).
A3.13.3.2 The master equation for collisional and radiative energy redistribution under conditions of generalized first-order kinetics
There is one special class of reaction systems in which a simplification occurs. If collisional energy redistribution of some reactant occurs by collisions with an excess of heat bath atoms or molecules that are considered
kinetically structureless, and if furthermore the reaction is either unimolecular or occurs again with a reaction
partner M having an excess concentration, then one will have generalized first-order kinetics for populations
pj of the energy levels of the reactant, i.e. with
dpj
=
dt
k=j
(Kj k pk Kkj pj ) kj pj
pj = cj
ck
k
(A3.13.24)
(A3.13.25)
In equation (A3.13.24), kj is the specific rate constant for reaction from level j , and Kj k are energy transfer
rate coefficients. With appropriate definition of a rate coefficient matrix K one has, in matrix notation,
dp
= Kp
dt
where for j = i
Kj i (T ) =
8kB T
1/2
[M]
(A3.13.26)
(A3.13.27)
Kkj (T ).
(A3.13.28)
k=j
The master equation (A3.13.26) applies also, under certain conditions, to radiative excitation with rate coefficients for radiative energy transfer being given by equations (A3.13.13)(A3.13.19), depending on the case, or
else by more general equations [10]. Finally, the radiative and collisional rate coefficients may be considered
together to be important at the same time in a given reaction system, if time scales for these processes are of
the appropriate order of magnitude.
The solution of equation (A3.13.26) is given by:
p(t) = exp(Kt)p(0).
(A3.13.29)
This solution can be obtained explicitly either by matrix diagonalization or by other techniques (see chapter A3.4 and [42, 43]). In many cases the discrete quantum level labels in equation (A3.13.24) can be replaced
by a continuous energy variable and the populations by a population density p(E), with replacement of the
sum by appropriate integrals [11]. This approach can be made the starting point of useful analytical solutions
for certain simple model systems [11, 19, 4446].
While the time dependent populations pj (t) may generally show a complicated behaviour, certain simple
limiting cases can be distinguished and characterized by appropriate parameters:
(a) The long time steady state limit (formally t ) is described by the largest eigenvalue 1 of K. Since
all j are negative, 1 has the smallest absolute value [35, 47]. In this limit one finds [47] (with the
reactant fraction FR = j pj ):
d ln( j pj (t))
d ln(FR (t))
=
= kuni = 1 .
dt
dt
(A3.13.30)
Thus, this eigenvalue 1 determines the unimolecular steady-state reaction rate constant.
(b) The second largest eigenvalue 2 determines ideally the relaxation time towards this steady state, thus:
1
= 2 .
relax
(A3.13.31)
More generally, further eigenvalues must be taken into account in the relaxation process.
(c) It is sometimes useful to define an incubation time inc by the limiting equation for steady state:
ln(FRst (t)) = 1 (t inc ).
(A3.13.32)
Figure A3.13.2 illustrates the origin of these quantities. Refer to [47] for a detailed mathematical
discussion as well as the treatment of radiative laser excitation, in which incubation phenomena are
important. Also refer to [11] for some classical examples in thermal systems.
Figure A3.13.2. Illustration of the analysis of the master equation in terms of its eigenvalues 1 and 2 for the example
of IR-multiphoton excitation. The dashed lines give the long time straight line limiting behaviour. The full line to the
right-hand side is for x = FR (t) with a straight line of slope 1 = kuni . The intercept of the corresponding dashed line
1
(FRSt ) indicates inc (see equation (A3.13.32)). The left-hand line is for x = |FR FRSt | with limiting slope 2 = relax
(see text and [47]).
As a rule, in thermal unimolecular reaction systems at modest temperatures, 1 is well separated from
the other eigenvalues, and thus the time scales for incubation and relaxation are well separated from the
1
1
1
. On the other hand, at high temperatures, kuni , relax
and inc
steady-state reaction time scale reaction = kuni
may merge. This is illustrated in figure A3.13.3 for the classic example of thermal unimolecular dissociation
[4851]:
(A3.13.33)
N2 O + Ar N2 + O + Ar.
Note that in the low pressure limit of unimolecular reactions (chapter A3.4), the unimolecular rate constant
1
kuni is entirely dominated by energy transfer processes, even though the relaxation and incubation rates (relax
1
and inc ) may be much faster than kuni .
The master equation treatment of energy transfer in even fairly complex reaction systems is now well
established and fairly standard [52]. However, the rate coefficients Kij for the individual energy transfer
processes must be established and we shall discuss some aspects of this matter in the following section.
A3.13.3.3
Collisional energy transfer in molecules is a field in itself and is of relevance for kinetic theory (chapter A3.1),
gas phase kinetics (chapter A3.4), RRKM theory (chapter A3.12), the theory of unimolecular reactions in
general, as well as the kinetics of laser systems [53]. Chapters C3.3C3.5 treat these subjects in detail. We
summarize those aspects that are of importance for mechanistic considerations in chemically reactive systems.
We start from a model in which collision cross sections or rate constants for energy transfer are compared with a reference quantity such as average Lennard-Jones collision cross sections or the usually cited
1
1
Figure A3.13.3. Dissociation (kuni = kdiss ), incubation (inc
) and relaxation (relax
) rate constants for the reaction
N2 O N2 + O at low pressure in argon (from [11], see discussion in the text for details and references to the experiments).
8kB T
AB
1/2
(2,2)
AB
(A3.13.34)
AB
r
12
AB
r
(A3.13.35)
Given such a reference, we can classify various mechanisms of energy transfer either by the probability that a
certain energy transfer process will occur in a Lennard-Jones reference collision, or by the average energy
transferred by one Lennard-Jones collision.
With this convention, we can now classify energy transfer processes either as resonant, if | Et | defined
in equation (A3.13.8) is small, or non-resonant, if it is large. Quite generally the rate of resonant processes
can approach or even exceed the Lennard-Jones collision frequency (the latter is possible if other long-range
potentials are actually applicable, such as by permanent dipoledipole interaction).
Resonant processes of some importance include resonant electronic to electronic energy transfer (EE),
such as the pumping process of the iodine atom laser
(EE)
O2 (1 ) + I(2 P3/2 ) O2 (3
g )
+ I(2 P1/2 ).
(A3.13.36)
Another near resonant process is important in the hydrogen fluoride laser, equation (A3.13.37), where vibrational to vibrational energy transfer is of interest:
v) + HF(v
v),
(A3.13.37)
where v is the number of vibrational quanta exchanged. If HF were a harmonic oscillator, Et would be
zero (perfect resonance). In practice, because of anharmonicity, the most important process is exothermic,
leading to increasing excitation v of some of the HF molecules with successive collisions [55, 56], because
the exothermicity drives this process to high v as long as plenty of HF(v ) with low v are available.
Resonant rotational to rotational (RR) energy transfer may have rates exceeding the Lennard-Jones
collision frequency because of long-range dipoledipole interactions in some cases. Quasiresonant vibration
to rotation transfer (VR) has recently been discussed in the framework of a simple model [57].
Non-resonant processes include vibrationtranslation (VT) processes with transfer probabilities decreasing to very small values for diatomic molecules with very high vibrational frequencies, of the order of
104 and less for the probability of transferring a quantum in a collision. Also, vibration to rotation (VR)
processes frequently have low probabilities, of the order of 102 , if Et is relatively large. Rotation to translation (RT) processes are generally fast, with probabilities near 1. Also, the RVT processes in collisions of
large polyatomic molecules have high probabilities, with average energies transferred in one Lennard-Jones
collision being of the order of a few kJ mol1 [11, 25], or less in collisions with rare gas atoms. As a general
rule one may assume collision cross sections to be small, if Et is large [11, 58, 59].
In the experimental and theoretical study of energy transfer processes which involve some of the
above mechanisms, one should distinguish processes in atoms and small molecules and in large polyatomic
molecules. For small molecules a full theoretical quantum treatment is possible and even computer program
packages are available [6063], with full state to state characterization. A good example are rotational energy
transfer theory and experiments on He + CO [64]:
He + CO(j ) He + CO(j ).
(A3.13.38)
On the experimental side, small molecule energy transfer experiments may use molecular beam techniques
[6567] (see also chapter C3.3 for laser studies).
In the case of large molecules, instead of the detailed quantum state characterization implied in the
cross sections fi and rate coefficients Kfi of the master equation (A3.13.24), one derives more coarse grained
information on levels covering a small energy bandwidth around E and E (with an optional notation
KFI (E , E)) or finally energy transfer probabilities P (E , E) for a transition from energy E to energy E
in a highly excited large polyatomic molecule where the density of states (E ) is very large, for example
in a collision with a heat bath inert gas atom [11]. Such processes can currently be modelled by classical
trajectories [6870].
Experimental access to the probabilities P (E , E) for energy transfer in large molecules usually involves
techniques providing just the first moment of this distribution, i.e. the average energy E transferred in a
collision. Such methods include UV absorption, infrared fluorescence and related spectroscopic techniques
[11, 28, 7174]. More advanced techniques, such as kinetically controlled selective ionization (KCSI [74])
have also provided information on higher moments of P (E , E), such as ( E)2 .
The standard mechanisms of collisional energy transfer for both small and large molecules have been
treated extensively and a variety of scaling laws have been proposed to simplify the complicated body of data
[58, 59, 75]. To conclude, one of the most efficient special mechanisms for energy transfer is the quasi-reactive
process involving chemically bound intermediates, as in the example of the reaction:
O2 (v , j ) + O O3 O2 (v , j ) + O.
(A3.13.39)
Such processes transfer very large amounts of energy in one collision and have been treated efficiently by the
statistical adiabatic channel model [11, 19, 30, 7679]. They are quite similar mechanistically to chemical
activation systems. One might say that in such a mechanism one may distinguish three phases:
(a) Formation of a bound collision complex AB:
A(v , j ) + B AB .
(A3.13.40)
AB AB .
(A3.13.41)
AB A(v , j ) + B.
(A3.13.42)
That is, rapid IVR in the long lived intermediate is an essential step. We shall treat this important process
in the next section, but mention here in passing the observation of so-called supercollisions transferring
large average amounts of energy E in one collision [80], even if intermediate complex formation may not
be important.
A3.13.4
In this section we review our understanding of IVR as a special case of intramolecular energy transfer.
The studies are based on calculations of the time evolution of vibrational wave packets corresponding to
middle size and large amplitude vibrational motion in polyatomic molecules. An early example for the
investigation of wave packet motion as a key to understanding IVR and its implication on reaction kinetics
using experimental data is given in [81]. Since then, many other contributions have helped to increase our
knowledge using realistic potential energy surfaces, mainly for two- and three-dimensional systems, and we
give a brief summary of these results below.
A3.13.4.1
Before undergoing a substantial and, in many cases, practically irreversible, change of geometrical structure
within a chemical reaction, a molecule may often perform a series of vibrations in the multidimensional
space around its equilibrium structure. This applies in general to reactions that take place entirely in the
bound electronic ground state and in many cases to reactions that start in the electronic ground state near the
equilibrium structure, but evolve into highly excited states above the reaction threshold energy. In the latter
case, within the general scheme of equation (A3.13.1) a reaction is thought to be induced by a sufficiently
energetic pulse of electromagnetic radiation or by collisions with adequate high-energy collision partners. In
the first case, a reaction is thought to be the last step after a chain of excitation steps has transferred enough
energy into the molecule to react either thermally, by collisions, or coherently, for instance by irradiation with
infrared laser pulses. These pulses can be tuned to adequately excite vibrations along the reaction coordinate,
the amplitudes of which become gradually larger until the molecule undergoes a sufficiently large structural
change leading to the chemical reaction.
Vibrational motion is thus an important primary step in a general reaction mechanism and detailed
investigation of this motion is of utmost relevance for our understanding of the dynamics of chemical reactions.
In classical mechanics, vibrational motion is described by the time evolution q(t)
and p(t)
of general internal
position and momentum coordinates. These time dependent functions are solutions of the classical equations
0 ) = p0 . The definition of
of motion, e.g. Newtons equations for given initial conditions q(t
0 ) = q0 and p(t
initial conditions is generally limited in precision to within experimental uncertainties q0 and p0 , more
p p(t)),
initial distribution F0 (q q0 , p p0 ), with widths q0 and p0 and the time evolution Ft (q q(t),
which may be quite different from the initial distribution F0 , depending on the integrability of the dynamical
system. Ideally, for classical, integrable systems, vibrational motion may be understood as the motion of
narrow, well localized distributions F (q q(t),
p p(t))
In time-dependent quantum mechanics, vibrational motion may be described as the motion of the wave packet
|(q, t)|2 in configuration space, e.g. as defined by the possible values of the position coordinates q. This
motion is given by the time evolution of the wave function (q, t), defined as the projection q|(t) of
the time-dependent quantum state |(t) on configuration space. Since the quantum state is a complete
description of the system, the wave packet defining the probability density can be viewed as the quantum
mechanical counterpart of the classical distribution F (q q(t),
p p(t)).
h d|(t)
= H |(t)
2 dt
(A3.13.43)
where h is the Planck constant and H is the Hamiltonian of the system under consideration. Solutions depend
on initial conditions |(t0 ) and may be formulated using the time evolution operator U (t, t0 ):
|(t) = U (t, t0 )|(t0 ) .
(A3.13.44)
Alternatively, in the case of incoherent (e.g. statistical) initial conditions, the density matrix operator P (t) =
|(t) (t)| at time t can be obtained as the solution of the Liouvillevon Neumann equation:
P (t) = U (t, t0 )P (t0 )U (t, t0 )
(A3.13.45)
where U (t, t0 ) is the adjoint of the time evolution operator (in strictly conservative systems, the time evolution
operator is unitary and U (t, t0 ) = U 1 (t, t0 ) = U (t0 , t)).
The calculation of the time evolution operator in multidimensional systems is a formidable task and some
results will be discussed in this section. An alternative approach is the calculation of semi-classical dynamics as
demonstrated, among others, by Heller [8688], Marcus [89, 90], Taylor [91, 92], Metiu [93, 94] and coworkers
(see also [83] as well as the review by Miller [95] for more general aspects of semiclassical dynamics). This
method basically consists of replacing the -function distribution in the true classical calculation by a Gaussian
distribution in coordinate space. It allows for a simulation of the vibrational quantum dynamics to the extent
that interference effects in the evolving wave packet can be neglected. While the application of semi-classical
methods might still be of some interest for the simulation of quantum dynamics in large polyatomic molecules
in the near future, as a natural extension of classical molecular dynamics calculations [68, 96], full quantum
mechanical calculations of the wave packet evolution in smaller polyatomic molecules are possible with the
currently available computational resources. Following earlier spectroscopic work and three-dimensional
quantum dynamics results [81, 97100], Wyatt and coworkers have recently demonstrated applications of
full quantum calculations to the study of IVR in fluoroform, with nine degrees of freedom [101, 102] and in
benzene [103], considering all 30 degrees of freedom [104]. Such calculations show clearly the possibilities
in the computational treatment of quantum dynamics and IVR. However, remaining computational limitations
restrict the study to the lower energy regime of molecular vibrations, when all degrees of freedom of systems
with more than three dimensions are treated. Large amplitude motion, which shows the inherently quantum
mechanical nature of wave packet motion and is highly sensitive to IVR, cannot yet be discussed for such
molecules, but new results are expected in the near future, as indicated in recent work on ammonia [105, 106],
formaldehyde and hydrogen peroxide [106108], and hydrogen fluoride dimer [109111] including all six
internal degrees of freedom.
A key feature in quantum mechanics is the dispersion of the wave packet, i.e. the loss of its Gaussian
shape. This feature corresponds to a delocalization of probability density and is largely a consequence of
anharmonicities of the potential energy surface, both the diagonal anharmonicity, along the manifold in which
the motion started, and off diagonal, induced by anharmonic coupling terms between different manifolds in
the Hamiltonian. Spreading of the wave packet into different manifolds is thus a further important feature of
IVR. In [84, 85] this type of IVR was called delocalization quantum intramolecular vibrational redistribution
(DIVR). DIVR plays a central role for the understanding of statistical theories for unimolecular reactions in
polyatomic molecules [84, 97], as will be discussed below.
A3.13.4.3
As in classical mechanics, the outcome of time-dependent quantum dynamics and, in particular, the occurrence
of IVR in polyatomic molecules, depends both on the Hamiltonian and the initial conditions, i.e. the initial
quantum mechanical state |(t0 ) . We focus here on the time-dependent aspects of IVR, and in this case
such initial conditions always correspond to the preparation, at a time t0 , of superposition states of molecular
(spectroscopic) eigenstates involving at least two distinct vibrational energy levels. Strictly, IVR occurs
if these levels involve at least two distinct vibrational manifolds in terms of which the total (vibrational)
Hamiltonian is not separable [84]. In a time-independent view, this requirement states that the wave functions
belonging to the two spectroscopic states are spread in a non-separable way over the configuration space
spanned by at least two different vibrational modes. The conceptual framework for the investigation of IVR
may be sketched within the following scheme, which also mirrors the way we might investigate IVR in the
time-dependent approach, both theoretically and experimentally:
|(t1 )
|(t0 )
U free (t,t0 )
|(t) .
(A3.13.46)
In a first time interval [t1 , t0 ] of the scheme (A3.13.46), a superposition state is prepared. This step corresponds to the step in equation (A3.13.1). One might think of a time evolution |(t1 ) |(t0 ) =
U prep (t0 , t1 )|(t1 ) , where |(t1 ) may be a molecular eigenstate and U prep is the time evolution operator
obtained from the interaction with an external system, to be specified below. The probability distribution
|(q, t0 )|2 is expected to be approximatively localized in configuration space, such that |(q , t0 )|2 > 0 for
position coordinates q M belonging to some specific manifold M and |(q, t0 )|2 0 for coordinates
q M belonging to the complementary manifold M = M . In a second time interval [t0 , t1 ], the superposition state |(t0 ) has a free evolution into states |(t) = U free (t, t0 )|(t0 ) . This step corresponds to the
intermediate step equation (A3.13.47), occurring between the steps described before by equations (A3.13.1)
and (A3.13.2) (see also equation (A3.13.41)):
R R .
(A3.13.47)
IVR is present if |(q, t)|2 > 0 is observed for t > t0 also for q M. IVR may of course also occur during
the excitation process, if its time scale is comparable to that of the excitation.
In the present section, we concentrate on coherent preparation by irradiation with a properly chosen
laser pulse during a given time interval. The quantum state at time t1 may be chosen to be the vibrational
(g)
ground state |0 in the electronic ground state. In principle, other possibilities may also be conceived for the
preparation step, as discussed in sections A3.13.1A3.13.3. In order to determine superposition coefficients
within a realistic experimental set-up using irradiation, the following questions need to be answered: (1) What
are the eigenstates? (2) What are the electric dipole transition matrix elements? (3) What is the orientation
of the molecule with respect to the laboratory fixed (linearly or circularly) polarized electric field vector of
the radiation? The first question requires knowledge of the potential energy surface, or the Hamiltonian
H 0 (p, q) of the isolated molecule, the second that of the vector valued surface (q) of the electric dipole
moment. This surface yields the operator, which couples spectroscopic states by the impact of an external
irradiation field and thus directly affects the superposition procedure. The third question is indeed of great
importance for comparison with experiments aiming at the measurement of internal wave packet motion in
polyatomic molecules and has recently received much attention in the treatment of molecular alignment and
orientation [112, 113], including non-polar molecules [114, 115]. To the best of our knowledge, up to now
explicit calculations of multidimensional wave packet evolution in polyatomic molecules have been performed
upon neglect of rotational degrees of freedom, i.e. only internal coordinates have been considered, although
calculations on coherent excitation in ozone level structures with rotation exist [116, 117], which could be
interpreted in terms of wave packet evolution. A more detailed discussion of this point will be given below
for a specific example.
A3.13.4.4
There are numerous methods for solving the time dependent Schrodinger equation (A3.13.43), and some
of them were reviewed by Kosloff [118] (see also [119, 120]). Whenever projections of the evolving wave
function on the spectroscopic states are useful for the detailed analysis of the quantum dynamics (and this
is certainly the case for the detailed analysis of IVR), it is convenient to express the Hamiltonian based on
spectroscopic states |n :
h
n |n n |
(A3.13.48)
H 0 =
2
n
where n are the eigenfrequencies. For an isolated molecule H = H 0 in equation (A3.13.43) and the time
evolution operator is of the form
U (t, t0 ) =
n
exp(in (t t0 ))|n n |.
(A3.13.49)
(A3.13.50)
Here, n (q) = q|n are the wave functions of the spectroscopic states and the coefficients cn0 are determined
from the initial conditions
(q, t0 ) =
n
cn0 n (q),
cn0 = n |(t0 ) .
(A3.13.51)
Equation (A3.13.49) describes the spectroscopic access to quantum dynamics. Clearly, when the spectral
structure becomes too congested, i.e. when there are many close lying frequencies n , calculation of all
spectroscopic states becomes difficult. However, often it is not necessary to calculate all states when certain
model assumptions can be made. One assumption concerns the separation of time scales. When there
is evidence for a clear separation of time scales for IVR, only part of the spectroscopic states need to be
considered for fast evolution. Typically, these states have large frequency separations, and considering only
such states means neglecting the fine-grained spectral structure as a first approximation. An example for
separation of time scales is given by the dynamics of the alkyl CH chromophore in CHXYZ compounds,
which will be discussed below. This group span a three-dimensional linear space of stretching and bending
vibrations. These vibrations are generally quite strongly coupled, which is manifested by the occurrence of a
Fermi resonance in the spectral structure throughout the entire vibrational energy space. As we will see, the
corresponding time evolution and IVR between these modes takes place in less than 1 ps, while other modes
become involved in the dynamics on much longer time scales (10 ps to ns, typically). The assumption for
time scale separation and IVR on the subpicosecond time scale for the alkyl CH chromophore was founded
on the basis of spectroscopic data nearly 20 years ago [98, 121]. The first results on the nature of IVR in
the CH chromophore system and its role in IR photochemistry were also reported by that time [122, 123],
including results for the acetylenic CH chromophore [124] and results obtained from first calculations of
the wave packet motion [81]. The validity of this assumption has recently been confirmed in the case of
CHF3 both experimentally, from the highly resolved spectral structure of highly excited vibrational overtones
[125, 126], and theoretically, including all nine degrees of freedom for modestly excited vibrational overtones
up to 6000 cm1 [102].
A3.13.4.5
Modern photochemistry (IR, UV or VIS) is induced by coherent or incoherent radiative excitation processes
[47]. The first step within a photochemical process is of course a preparation step within our conceptual
framework, in which time-dependent states are generated that possibly show IVR. In an ideal scenario, energy
from a laser would be deposited in a spatially localized, large amplitude vibrational motion of the reacting
molecular system, which would then possibly lead to the cleavage of selected chemical bonds. This is
basically the central idea behind the concepts for a mode selective chemistry, introduced in the late 1970s
[127], and has continuously received much attention [10, 117, 122, 128135]. In a recent review [136], IVR
was interpreted as a molecular enemy of possible schemes for mode selective chemistry. This interpretation
is somewhat limited, since IVR represents more complex features of molecular dynamics [37, 84, 134], and
even the opposite situation is possible. IVR can indeed be selective with respect to certain structural features
[85, 97] that may help mode selective reactive processes after tailored laser excitation [137].
To be more specific, we assume that for a possible preparation step the Hamiltonian might be given
during the preparation time interval [t1 , t0 ] by the expression:
H = H 0 + H i (t)
(A3.13.52)
where H 0 is the Hamiltonian of the isolated molecule and H i is the interaction Hamiltonian between the
molecule and an external system. In this section, we limit the discussion to the case where the external system
is the electromagnetic radiation field. For the interaction with a classical electromagnetic field with electric
field vector E(t), the interaction Hamiltonian is given by the expression:
E(t).
H i (t) =
(A3.13.53)
is the operator of the electric dipole moment. When we treat the interaction with a classical field in
where
this way, we implicitly assume that the field will remain unaffected by the changes in the molecular system
under consideration. More specifically, its energy content is assumed to be constant. The energy of the
radiation field is thus not explicitly considered in the expression for the total Hamiltonian and all operators
acting on states of the field are replaced by their time-dependent expectation values. These assumptions are
widely accepted, whenever the number of photons
in each field mode is sufficiently large. For a coherent,
2
2
monochromatic, polarized field with intensity I =
in vacuo, which is a typical
0 /0 |E| 1 MW cm
value used in laser chemical experiments in the gas phase at low pressures, the number N of mid infrared
photons existing in a cavity of volume V = 1 m3 is [138, p 498]:
N =
IV
1021 .
c0 h
(A3.13.54)
Equation (A3.13.54) legitimates the use of this semi-classical approximation of the moleculefield interaction
in the low-pressure regime.
Since H i (t) is explicitly time dependent, the time evolution operator is more complicated than in equation A3.13.49. However, the time-dependent wave function can still be written in the form
(q, t) =
cn (t)n (q)
(A3.13.55)
with time-dependent coefficients that are obtained by solving the set of coupled differential equations
i
dcn (t)
=
dt
(A3.13.56)
where Wnn = nn n (nn is the Kronecker symbol, n were defined in equation (A3.13.48)) and
2
n |H i (t)|n
h
2
n E(t).
=
n ||
h
Vnn (t) =
(A3.13.57)
I0 /MW cm2 ,
(A3.13.58)
where is the direction of the electric field vector of the linearly polarized radiation field with maximal intensity
I0 . The solution of equation (A3.13.56) may still be quite demanding, depending on the size of the system
under consideration. However, it has become a practical routine procedure to use suitable approximations
such as the QRA (quasiresonant approximation) or Floquet treatment [35, 122, 129] and programmes for the
numerical solution are available [139, 140].
A3.13.4.6
At this stage we may distinguish between excitation involving different electronic states and excitation occurring within the same electronic (ground) state. When the spectroscopic states are located in different electronic
states, say the ground (g) and excited (e) states, one frequently assumes the FranckCondon approximation
to be applicable:
(e) ge (g) | (e) .
n(g) ||
(A3.13.59)
n
n
n
Such electronic excitation processes can be made very fast with sufficiently intense laser fields. For example,
if one considers monochromatic excitation with a wavenumber in the UV region (60 000 cm1 ) and a coupling
strength (ge E)/ hc 4000 cm1 (e.g. ge 1 Debye in equation (A3.13.59), I 50 TW cm2 ), excitation
occurs within 1 fs [141]. During such a short excitation time interval the relative positions of the nuclei remain
unchanged (Franck approximation). Within these approximations, if one starts the preparation step in the
(g)
vibrational ground state |0 , the resulting state |(t0 ) at time t0 has the same probability distribution as the
vibrational ground state. However, it is now transferred into the excited electronic state where it is no longer
stationary, since it is a superposition state of vibrational eigenstates in the excited electronic state:
(g)
|(t0 ) =
n(e) |0 |n(e) .
(A3.13.60)
Often the potential energy surfaces for the ground and excited states are fairly different, i.e. with significantly
different equilibrium positions. The state |(t0 ) will then correspond to a wave packet, which has nearly
a Gaussian shape with a centre position that is largely displaced from the minimal energy configuration on
the excited surface and, since the Franck approximation can be applied, the expectation value of the nuclear
linear momentum vanishes. In a complementary view, the superposition state of equation (A3.13.60) defines
the manifold M in configuration space. It is often referred to as the bright state, since its probability
density defines a region in configuration space, the FranckCondon region, which has been reached by the
irradiation field through mediation by the electric dipole operator. After the preparation step, the wave packet
most likely starts to move along the steepest descent path from the FranckCondon region. One possibility is
that it proceeds to occupy other manifolds, which were not directly excited. The occupation of the remaining,
dark manifolds (e.g. M ) by the time-dependent wave packet is a characteristic feature of IVR.
Studies of wave packet motion in excited electronic states of molecules with three and four atoms were
conducted by Schinke, Engel and collaborators, among others, mainly in the context of photodissociation
dynamics from the excited state [142144] (for an introduction to photodissociation dynamics, see [7], and
also more recent work [145149] with references cited therein). In these studies, the dissociation dynamics
is often described by a time-dependent displacement of the Gaussian wave packet in the multidimensional
configuration space. As time goes on, this wave packet will occupy different manifolds (from where the
molecule possibly dissociates) and this is identified with IVR. The dynamics may be described within the
Gaussian wave packet method [150], and the vibrational dynamics is then of the classical IVR type (CIVR
[84]). The validity of this approach depends on the dissociation rate on the one hand, and the rate of
delocalization of the wave packet on the other hand. The occurrence of DIVR often receives less attention in
the discussions of photodissociation dynamics mentioned above. In [148], for instance, details of the wave
packet motion by means of snapshots of the probability density are missing, but a delocalization of the wave
packet probably takes place, as may be concluded from inspection of figure 5 therein.
A3.13.5 IVR in the electronic ground state: the example of the CH chromophore
A3.13.5.1
A system that shows IVR with very fast spreading of the wave packet, i.e. DIVR in the subpicosecond
time range, is that of the infrared alkyl CH chromophore, which will be used in the remaining part of this
chapter to discuss IVR as a result of a mode specific excitation within the electronic ground state. The CH
stretching and bending modes of the alkyl CH chromophore in CHXYZ compounds are coupled by a generally
strong Fermi resonance [100, 151]. Figure A3.13.4 shows the shape of the potential energy surface for the
symmetrical compound CHD3 as contour line representations of selected one- and two-dimensional sections
(see figure caption for a detailed description). The important feature is the curved shape of the V (Qs , Qb1 )
potential section (V (Qs , Qb2 ) being similarly curved), which indicates a rather strong anharmonic coupling.
This feature is characteristic for compounds of the type CHXYZ [84, 100, 151153]. Qs , Qb1 and Qb2 are
(mass weighted) normal coordinates of the CH stretching and bending motion, with symmetry A1 and E,
Figure A3.13.4. Potential energy cuts along the normal coordinate subspace pertaining to the CH chromophore in CHD3 .
Qb1 is the A coordinate in Cs symmetry, essentially changing structure along the x-axis (see also figure A3.13.5), and
Qb2 is the A coordinate, essentially changing structure along the y-axis. Contour lines show equidistant energies at wave
number differences of 3000 cm1 up to 30 000 cm1 . The upper curves are one-dimensional cuts along Qb2 (left) and Qs
(right). The dashed curves in the two upper figures show harmonic potential curves (from [154]).
respectively, in the C3v point group of symmetrical CHD3 . A change of Qs is a concerted motion of all atoms
along the z-axis, defined in figure A3.13.5. However, displacements along Qs are small for the carbon and
deuterium atoms, and large for the hydrogen atom. Thus, this coordinate essentially describes a stretching
motion of the CH bond (along the z-axis). In the same way, Qb1 and Qb2 describe bending motions of the
CH bond along the x- and y-axis, respectively (see figure A3.13.5). In the one-dimensional sections the
positions of the corresponding spectroscopic states are drawn as horizontal lines. On the left-hand side, in
the potential section V (Qb2 ), a total of 800 states up to an energy equivalent wave number of 25 000 cm1
has been considered. These energy levels may be grouped into semi-isoenergetic shells defined by multiplets
of states with a constant chromophore quantum number N = vs + 21 vb = 0, 21 , 1, 23 , 2, 25 , . . ., where vs and
vb are quantum numbers of effective basis states (Fermi modes [97, 152, 154]) that are strongly coupled by
a 2:1 Fermi resonance. These multiplets give rise to spectroscopic polyads and can be well distinguished in
the lower energy region, where the density of states is low.
In the potential section V (Qs ), shown on the right hand side of Figure A3.13.4, the subset of A1 energy
states is drawn. This subset contains only multiplets with integer values of the chromophore quantum number
N = 0, 1, 2, . . .. This reduction allows for an easier visualization of the multiplet structure and also represents
H
y
C
D
Figure A3.13.5. Coordinates and axes used to describe the wave packet dynamics of the CH chromophore in CHX3 or
CHXYZ compounds.
the subset of states that are strongly coupled by the parallel component of the electric dipole moment (see
discussion in the following paragraph). The excitation dynamics of the CH chromophore along the stretching
manifold can indeed be well described by restriction to this subset of states [97, 154].
Excitation specificity is a consequence of the shape of the electric dipole moment surface. For the alkyl
CH chromophore in CHX3 compounds, the parallel component of the dipole moment, i.e. the component
parallel to the symmetry axis, is a strongly varying function of the CH stretching coordinate, whereas it
changes little along the bending manifolds [155, 156]. Excitation along this component will thus induce
preparation of superposition states lying along the stretching manifold, preferentially. These states thus
constitute the bright manifold in this example. The remaining states define the dark manifolds and any
substantial population of these states during or after such an excitation process can thus be directly linked
to the existence of IVR. On the other hand, the perpendicular components of the dipole moment vector are
strongly varying functions of the bending coordinates. For direct excitation along one of these components,
states belonging to the bending manifolds become the bright states and any appearance of a subsequent
stretching motion can be interpreted as arising from IVR.
The following discussion shall illustrate our understanding of structural changes along dark manifolds
in terms of wave packet motion as a consequence of IVR. Figure A3.13.6 shows the evolution of the wave
packet for the CH chromophore in CHF3 during the excitation step along the parallel (stretching) coordinate
[97]. The potential surface in the CH chromophore subspace is similar to that for CHD3 (figure A3.13.4
above), with a slightly more curved form in the stretchingbending representation (figures are shown in
[97, 151]). The laser is switched on at a given time t1 , running thereafter as a continuous, monochromatic
irradiation up to time t0 , when it is switched off. Thus, the electric field vector is given as
E(t) = h(t t1 )h(t0 t)E0 cos(L t).
(A3.13.61)
where h(t) is the Heaviside unit step function, E0 is the amplitude of the electric field vector and L = 2 c L
its angular frequency. Excitation parameters are the irradiation intensity I0 = 30 TW cm2 , which corresponds
to a maximal electric field strength E0 3.4 1010 V m1 , and wave number L = 2832.42 cm1 , which
lies in the region of the fundamental for the CH stretching vibration (see arrows in the potential cut V (Qs )
of figure (A3.13.4)). The figure shows snapshots of the time evolution of the wave packet between 50 and
70 fs after the beginning of the irradiation (t1 = 0 here). On the left-hand side, contour maps of the
Figure A3.13.6. Time evolution of the probability density of the CH chromophore in CHF3 after 50 fs of irradiation with
an excitation wave number L = 2832.42 cm1 at an intensity I0 = 30 TW cm2 . The contour lines of equiprobability
density in configuration space have values 2 105 u1 pm2 for the lowest line shown and distances between the
lines of 24, 15, 29 and 20 105 u1 pm2 in the order of the four images shown. The averaged energy of the wave
packet corresponds to 6000 cm1 (roughly 3100 cm1 absorbed) with a quantum mechanical uncertainty of 3000 cm1
(from [97]).
|(Qs , Qb , b , t)|2 db
(A3.13.62)
are shown, where Qs is the coordinate for the stretching motion and Qb = Q2b1 + Q2b2 , b = arctan(Qb2 /Qb1 )
are polar representations of the bending coordinates Qb1 and Qb2 . Additionally, contour curves of the potential
energy surface are drawn at the momentary energy of the wave packet. This energy is defined as:
E(t) =
n
where
En pn (t)
(A3.13.63)
(A3.13.64)
are the time-dependent populations of the spectroscopic states during the preparation step (the complex
coefficients cn (t) in equation (A3.13.64) are calculated according to equation (A3.13.55), the spectroscopic
h
n are defined in equation (A3.13.48); the dashed curves indicate the quantum mechanical
energies En = 2
uncertainty which arises from the superposition of molecular eigenstates). The same evolution is repeated on
the right-hand side of the figure as a three-dimensional representation.
In the treatment adopted in [97], the motion of the CF3 frame is implicitly considered in the dynamics
of the normal modes. Indeed, the integrand |(Qs , Qb , b , t)|2 in equation (A3.13.62) is to be interpreted
as probability density for the change of the CHF3 structure in the subspace of the CH chromophore, as
defined by the normal coordinates Qs , Qb1 and Qb2 , irrespective of the molecular structure and its change
in the remaining space. This interpretation is also valid beyond the harmonic approximation, as long as the
structural change in the CH chromophore space can be dynamically separated from that of the rest of the
molecule. The assumption of dynamical separation is well confirmed, both from experiment and theory, at
least during the first 1000 fs of motion of the CH chromophore.
When looking at the snapshots in figure A3.13.6, we see that the position of maximal probability
oscillates
back and forth along the stretching coordinate between the walls at Qs = 20 and +25 u pm, with an
approximate period of 12 fs, which corresponds to the classical oscillation period = 1/ of a pendulum
with a frequency = c0 8.5 1013 s1 and wave number = 2850 cm1 . Indeed, the motion of the
whole wave packet approximately follows this oscillation and, when it does so, the wave packet motion is
semiclassical. In harmonic potential wells the motion of the wave packet is always semiclassical [157159].
However, since the potential surface of the CH chromophore is anharmonic, some gathering and spreading
out of the wave packet is observable on top of the semiclassical motion. It is interesting to note that, at this
initial stage of the excitation step, the motion of the wave packet is nearly semiclassical, though with modest
amplitudes of the oscillations, despite the anharmonicity of the stretching potential.
The later time evolution is shown in figure A3.13.7, between 90 and 100 fs, and in figure A3.13.8, between
390 and 400 fs, after the beginning of the excitation (time step t1 ). Three observations are readily made:
first, the amount of energy absorbed by the chromophore has increased, from 3000 cm1 in figure A3.13.6, to
6000 cm1 in figure A3.13.7 and 12 000 cm1 in figure A3.13.8. Second, the initially semiclassical motion
has been replaced by a more irregular motion of probability density, in which the original periodicity is hardly
visible. Third, the wave packet starts to occupy nearly all of the energetically available region in configuration
space, thus escaping from the initial, bright manifolds into the dark manifolds. From these observations,
the following conclusions may be directly drawn: IVR of the CH chromophore in fluoroform is fast (in the
subpicosecond time scale); IVR sets in already during the excitation process, i.e. when an external force field
is driving the molecular system along a well prescribed path in configuration space (the bright manifold);
IVR is of the delocalization type (DIVR). Understanding these observations is central for the understanding
of IVR and they are discussed as follows:
Figure A3.13.7. Continuation of the time evolution for the CH chromophore in CHF3 after 90 fs of irradiation (see also
figure A3.13.6). Distances between the contour lines are 10, 29, 16 and 9 105 u1 pm2 in the order of the four images
shown. The averaged energy of the wave packet corresponds to 9200 cm1 (roughly 6300 cm1 absorbed) with a quantum
mechanical uncertainty of 5700 cm1 (from [97]).
Figure A3.13.8. Continuation of the time evolution for the CH chromophore in CHF3 after 392 fs of irradiation (see also
figures A3.13.6 and A3.13.7). Distances between the contour lines are 14, 12, 13 and 14 105 u1 pm2 in the order
of the four images shown. The averaged energy of the wave packet corresponds to 15 000 cm1 (roughly 12 100 cm1
absorbed) with a quantum mechanical uncertainty of 5800 cm1 (from [97]).
(a) A more detailed analysis of quantum dynamics shows that the molecular system, represented by the
group of vibrations pertaining to the CH chromophore in this example, absorbs continuously more energy
as time goes on. Let the absorbed energy be Eabs = N,abs (h/2 )L , where N,abs is the mean number of
absorbed photons. Since the carrier frequency of the radiation field is kept constant at a value close to the
fundamental of the stretching oscillation, L N =1 N =0 (N being the chromophore quantum number
here), this means that the increase in absorbed energy is a consequence of the stepwise multiphoton excitation
process, in which each vibrational level serves as a new starting level for further absorption of light after it has
itself been significantly populated. This process is schematically represented, within the example for CHD3 ,
by the sequence of upright arrows shown on the right-hand side of figure A3.13.4. N,abs is thus a smoothly
increasing function of time.
(b) The disappearance of the semiclassical type of motion and, thus, the delocalization of the wave
packet, is understood to follow the onset of dephasing. With increasing energy, both the effective anharmonic
couplings between the bright stretching mode and the dark bending modes, as well as the diagonal anharmonicity of the bright mode increase. The larger the anharmonicity, the larger the deviation from a purely
harmonic behaviour, in which the wave packet keeps on moving in a semiclassical way. In quantum mechanics, the increase in anharmonicity of an oscillator leads to an effective broadening eff > 0 in the distribution
of frequencies of high-probability transitionsfor transitions induced by the electric dipole operator usually
those with a difference of 1 in the oscillator quantum number (for the harmonic oscillator eff = 0).
On the other hand, these are the transitions which play a major role in the stepwise multiphoton excitation
of molecular vibrations. A broadening of the frequency distribution invariably leads to a broadening of the
distribution of relative phases of the time-dependent coefficients cn (t) in equation (A3.13.55). Although the
sum in equation (A3.13.55) is entirely coherent, one might introduce an effective coherence time defined by:
c,eff = 1/ eff .
(A3.13.65)
For the stretching oscillations of the CH chromophore in CHF3 c,eff 100 fs. Clearly, typical coherence time
ranges depend on both the molecular parameters and the effectively absorbed amount of energy during the
excitation step, which in turn depends on the coupling strength of the moleculeradiation interaction. A more
detailed study of the dispersion of the wave packet and its relationship with decoherence effects was carried
out in [106]. In [97] an excitation process has been studied for the model of two anharmonically coupled,
resonant harmonic oscillators (i.e. with at least one cubic coupling term) but under similar conditions as for
the CH chromophore in fluoroform discussed here. When the cubic coupling parameter is chosen to be very
small compared with the diagonal parameters of the Hamilton matrix, the motion of the wave packet is indeed
semiclassical for very long times (up to 600 ps) and, moreover, the wave packet does probe the bending
manifold without significantly changing its initial shape. This means that, under appropriate conditions, IVR
can also be of the classical type within a quantum mechanical treatment of the dynamics. Such conditions
require, for instance, that the band width h eff be smaller than the resonance width (power broadening) of
the excitation process.
(c) The third observation, that the wave packet occupies nearly all of the energetically accessible region
in configuration space, has a direct impact on the understanding of IVR as a rapid promotor of microcanonical
equilibrium conditions. Energy equipartition preceding a possible chemical reaction is the main assumption
in quasiequilibrium statistical theories of chemical reaction dynamics (RRKM theory [161163], transition
state theory [164, 165] but also within the statistical adiabatic channel model [76, 77]; see also chapter A3.12
and further recent reviews on varied and extended forms of statistical theories in [25, 166172]). In the case
of CHF3 one might conclude from inspection of the snapshots at the later stage of the excitation dynamics
(see figure A3.13.8) that after 400 fs the wave packet delocalization is nearly complete. Moreover, this
delocalization arises here from a fully coherent, isolated evolution of a system consisting of one molecule
and a coherent radiation field (laser). Of course, within the common interpretation of the wave packet
as a probability distribution in configuration space, this result means that, for an ensemble of identically
prepared molecules, vibrational motion is essentially delocalized at this stage and vibrational energy is nearly
equipartitioned.
However, the wave packet does not occupy all of the energetically accessible region. A more detailed
analysis of populations [97, table IV] reveals that, during the excitation process, the absorbed energy is
inhomogeneously distributed among the set of molecular eigenstates of a given energy shell (such a shell is
represented by all nearly iso-energetic states belonging to one of the multiplets shown on the right-hand side
of figure A3.13.4). Clearly, equipartition of energy is attained, if all states of an energy shell are equally
populated. The microcanonical probability distribution in configuration space may then be represented by a
typical member of the microcanonical ensemble, defined e.g. by the wave function
micro
1
Nshell
nshell
exp(inrandom )n
(A3.13.66)
where Nshell denotes the number of nearly iso-energetic states n of a shell and nrandom is a random phase. Such a
state is shown in figure A3.13.9. When comparing this state with the state generated by multiphoton excitation,
the two different kinds of superposition that lead to these wave packets must, of course, be distinguished. In
the stepwise multiphoton excitation, the time evolved wave packet arises from a superposition of many states
in several multiplets (with roughly constant averaged energy after some excitation time and a large energy
uncertainty). The microcanonical distribution is given by the superposition of states in a single multiplet (of
the same averaged energy but much smaller energy uncertainty). In the case of the CH chromophore in CHF3
studied in this example, the distribution of populations within a molecular energy shell is not homogeneous
during the excitation process because the multiplets are not ideally centred at the multiphoton resonance levels
and their energy range is effectively too large when compared to the resonance width of the excitation process
(power broadening). If molecular energy shells fall entirely within the resonance width of the excitation, such
as in the model systems of two harmonic oscillators studied in [97], population distribution within a shell
becomes more homogeneous [97, table V]. However, as discussed in that work, equidistribution of populations
does not imply that the wave packet is delocalized. Indeed, the contrary was shown to occur. If the probability
distribution in configuration space is to delocalize, the relative phases between the superposition states must
follow an irregular evolution, such as in a random phase ensemble, in addition to equidistribution of population.
Thus, one statement would therefore be that IVR is not complete, although very fast, during the multiphoton
excitation of CHF3 . Excitation and redistribution are indeed two concurring processes. In the limit of weak
field excitation, in the spectroscopic regime, the result is a superposition of essentially two eigenstates (the
ground and an excited state, for instance). Within the bright state concept, strong IVR will be revealed by an
instantaneous delocalization of probability density, both in the bright and the dark manifolds, as soon as
the excited state is populated, because the excited state is, of course, a superposition state of states from both
manifolds. On the other hand, strong field stepwise IR multiphoton excitation promotes, in a first step, the
deposition of energy in a spatially localized, time-dependent molecular structure. Simultaneously, IVR starts
to induce redistribution of this energy among other modes. The redistribution becomes apparent after some
time has passed and is expected to be of the DIVR type, at least on longer time scales. DIVR may lead to a
complete redistribution in configuration space, if the separation between nearly iso-energetic states is small
compared to the power broadening of the excitation field. However, under such conditions, at least during an
initial stage of the dynamics, CIVR will dominate.
In view of the foregoing discussion, one might ask what is a typical time evolution of the wave packet
for the isolated molecule, what are typical time scales and, if initial conditions are such that an entire energy
shell participates, does the wave packet resulting from the coherent dynamics look like a microcanonical
distribution? Such studies were performed for the case of an initially pure stretching Fermi mode (vs , vb =
0), with a high stretching quantum number, e.g. vs = 6. It was assumed that such a state might be prepared
by irradiation with some hypothetical laser pulse, without specifying details of the pulse. The energy of that
Figure A3.13.9. Probability density of a microcanonical distribution of the CH chromophore in CHF3 within the multiplet
with chromophore quantum number N = 6 (Nshell = N + 1 = 7). Representations in configuration space of stretching
(Qs ) and bending (Qb ) coordinates (see text following equation (A3.13.62) and figure A3.13.10). Left-hand side: typical
member of the microcanonical ensemble of the multiplet with N = 6 (random phases, equation (A3.13.66)). Right-hand
1
2
side: microcanonical density Pmicro = Nshell
nshell |n | for the multiplet with N = 6 (Nshell = 7). Adapted from [81].
state is located at the upper end of the energy range of the corresponding multiplet [81, 152, 154], which has
a total of Nshell = 7 states. Such a state couples essentially to all remaining states of that multiplet. The
corresponding evolution of the isolated system is shown as snapshots after the preparation step (t0 = 0) in
figure A3.13.10. The wave packet starts to spread out from the initially occupied stretching manifold (along
the coordinate axis denoted by Qs ) into the bending manifold (Qb ) within the first 3045 fs of evolution
(left-hand side). Later on, it remains delocalized most of the time (as shown at the time steps 80, 220 and
380 fs, on the right-hand side) with exceptional partial recovery of the initial conditions at some isolated times
(such as at 125 fs). The shape of the distribution at 220 fs is very similar to that of a typical member of the
microcanonical ensemble in figure A3.13.9 above. However, in Figure A3.13.9, the relative phases between
the seven superposition states were drawn from a random number generator, whereas in figure A3.13.10 they
result from a fully coherent and deterministic propagation of a wave function.
IVR in the example of the CH chromophore in CHF3 is thus at the origin of a redistribution process
which is, despite its coherent nature, of a statistical character. In CHD3 , the dynamics after excitation of the
stretching manifold reveals a less complete redistribution process in the same time interval [97]. The reason
for this is a smaller effective coupling constant ksbb between the Fermi modes of CHD3 (by a factor of four)
when compared to that of CHF3 . In [97] it was shown that redistribution in CHD3 becomes significant in the
picosecond time scale. However, on that time scale, the dynamical separation of time scales is probably no
longer valid and couplings to modes pertaining to the space of CD3 vibrations may become important and
have additional influence on the redistribution process.
A3.13.5.2
IVR in the CH chromophore system may also arise from excitation along the bending manifolds. Bending
motions in polyatomic molecules are of great importance as primary steps for reactive processes involving
isomerization and similar, large amplitude changes of internal molecular structure. At first sight, the onedimensional section of the potential surface along the out-of-plane CH bending normal coordinate in CHD3 ,
shown in figure A3.13.4, is clearly less anharmonic than its one-dimensional stretching counterpart, also shown
in that figure, even up to energies in the wave number region of 30 000 cm1 . This suggests that coherent
sequential multiphoton excitation of a CH bending motion, for instance along the x-axis in Figure A3.13.5,
la s e r o ff
0
Q
fs
Q
b
s
8 0
2 0
3 0
4 5
fs
fs
1 2 5
fs
2 2 0
fs
3 8 0
fs
fs
fs
Figure A3.13.10. Time-dependent probability density of the isolated CH chromophore in CHF3 . Initially, the system is
in a Fermi mode with six quanta of stretching and zero of bending motion. The evolution occurs within the multiplet
with chromophore quantum number N = 6 (Nshell = N + 1 = 7). Representations are given in the configuration
space of stretching (Qs ) and bending (Qb ) coordinates (see text following equation (A3.13.62): Qb is strictly a positive
quantity, and there is always a node at Qb = 0; the mirrored representation at Qb = 0 is artificial and serves to improve
visualization). Adapted from [81].
may induce a quasiclassical motion of the wave packet along that manifold [159, 160], which is significantly
longer lived than the motion induced along the stretching manifold under similar conditions (see discussion
above). Furthermore, the two-dimensional section in the CH bending subspace, spanned by the normal
coordinates in the lower part of figure A3.13.4, is approximately isotropic. This corresponds to an almost
perfect Cv symmetry with respect to the azimuthal angle (in the xy plane of figure A3.13.5), and is related to
the approximate conservation of the bending vibration angular momentum b [152, 173]. This implies that the
direct anharmonic coupling between the degenerate bending manifolds is weak. However, IVR between these
modes might be mediated by the couplings to the stretching mode. An interesting question is then to what extent
such a coupling scheme might lead to a motion of the wave packet with quasiclassical exchange of vibrational
energy between the two bending manifolds, following paths which could be described by classical vibrational
mechanics, corresponding to CIVR. Understanding quasiclassical exchange mechanisms of large amplitude
vibrational motion opens one desirable route of exerting control over molecular vibrational motion and reaction
dynamics. In [154] these questions were investigated by considering the CH bending motion in CHD3 and the
asymmetric isotopomers CHD2 T and CHDT2 . The isotopic substitution was investigated with the special goal
of a theoretical study of the coherent generation of dynamically chiral, bent molecular structures [174] and of
the following time evolution. It was shown that IVR is at the origin of a coherent racemization dynamics which
is superposed to a very fast, periodic exchange of left- and right-handed chiral structures (stereomutation
reaction, period of roughly 20 fs, comparable to the period of the bending motion) and sets in after typically
300500 fs. The main results are reviewed in the discussion of figures A3.13.11A3.13.13.
The wave packet motion of the CH chromophore is represented by simultaneous snapshots of twodimensional representations of the time-dependent probability density distribution
|sb (t, Qs , Qbi )|2 =
Qbj
(i = j )
(A3.13.67)
and
|bb (t, Qb1 , Qb2 )|2 =
Qs
(A3.13.68)
Such a sequence of snapshots, calculated in intervals of 4 fs, is shown as a series of double contour line plots on
the left-hand side of figure A3.13.11 (the outermost row shows the evolution of |bb |2 , equation (A3.13.68),
the innermost row is |sb |2 , equation (A3.13.67), at the same time steps). This is the wave packet motion
in CHD3 for excitation with a linearly polarized field along the the x-axis at 1300 cm1 and 10 TW cm2
after 50 fs of excitation. At this point a more detailed discussion regarding the orientational dynamics of
the molecule is necessary. Clearly, the polarization axis is defined in a laboratory fixed coordinate system,
while the bending axes are fixed to the molecular frame. Thus, exciting internal degrees of freedom along
specific axes in the internal coordinate system requires two assumptions: the molecule must be oriented or
aligned with respect to the external polarization axis, and this state should be stationary, at least during the
relevant time scale for the excitation process. It is possible to prepare oriented states [112, 114, 115] in the
gas phase, and such a state can generally be represented as a superposition of a large number of rotational
eigenstates. Two questions become important then: How fast does such a rotational superposition state
evolve? How well does a purely vibrational wave packet calculation simulate a more realistic calculation
which includes rotational degrees of freedom, i.e. with an initially oriented rotational wave packet? The
second question was studied recently by full dimensional quantum dynamical calculations of the wave packet
motion of a diatomic molecule during excitation in an intense infrared field [175], and it was verified that
rotational degrees of freedom may be neglected whenever vibrationalrotational couplings are not important
for intramolecular rotationalvibrational redistribution (IVRR) [84]. Regarding the first question, because of
the large rotational constant of methane, the time scales on which an initially oriented state of the free molecule
is maintained are likely to be comparatively short and it would also be desirable to carry out calculations that
CHD3
E~0
50
~x
k ;~
E~0
50
fs
54
fs
58
fs
62
fs
66
fs
b1
pQupm
70
;50
;50
50 ;20
Qb2 =pupm
50
Qs=pupm
650
pQb2
upm
fs
;50
50 ;20
Qb1 =pupm
- ;50
50
Qs=pupm
Figure A3.13.11. Illustration of the time evolution of reduced two-dimensional probability densities |bb |2 and |sb |2 ,
for the excitation of CHD3 between 50 and 70 fs (see [154] for further details). The full curve is a cut of the potential
energy surface at the momentary absorbed energy corresponding to 3000 cm1 during the entire time interval shown here
(6000 cm1 , if zero point energy is included). The dashed curves show the energy uncertainty of the time-dependent
wave packet, approximately 500 cm1 . Left-hand side: excitation along the x-axis (see figure A3.13.5). The vertical
axis in the two-dimensional contour line representations is the Qb1 -axis, the horizontal axes are Qb2 and Qs , for |bb |2
and |sb |2 , respectively. Right-hand side: excitation along the y-axis, but with the field vector pointing into the negative
y-axis. In the two-dimensional contour line representations, the vertical axis is the Qb2 -axis, the horizontal axes are Qb1
and Qs , for |bb |2 and |sb |2 , respectively. The lowest contour line has the value 44 105 u1 pm2 , the distance
between them is 7 105 u1 pm2 . Maximal values are nearly constant for all the images in this figure and correspond
to 140 105 u1 pm2 for |bb |2 and 180 105 u1 pm2 for |sb |2 .
b
Figure A3.13.12. Evolution of the probability for a right-handed chiral structure PR (t) (full curve, see equation (A3.13.69))
of the CH chromophore in CHD2 T (a) and CHDT2 (b) after preparation of chiral structures with multiphoton laser excitation, as discussed in the text (see also [154]). For comparison, the time evolution of PR according to a one-dimensional
model including only the Qb2 bending mode (dashed curve) is also shown. The left-hand side insert shows the time
evolution of PR within the one-dimensional calculations for a longer time interval; the right-hand insert shows the PR
time evolution within the three-dimensional calculation for the same time interval (see text).
include rotational states explicitly. Such calculations were done, for instance, for ozone at modest excitations
[116, 117], but they would be quite difficult for the methane isotopomers at the high excitations considered
in the present example.
The multiphoton excitation scheme corresponding to excitation along the x-axis is shown by the upright
arrows on the left-hand side of figure A3.13.4. In the convention adopted in [154], nuclear displacements
H
y
100
C
D
y
x
C
D
800
fs
804
fs
808
fs
812
fs
816
fs
6100
b2
pQupm
;100
;100
820
100 ;40
Qb1 =pupm
70
Qs=pupm
b2
pQupm
fs
;100
100 ;40
Qb1 =pupm
- ;100
70
Qs=pupm
Figure A3.13.13. Illustration of the time evolution of reduced two-dimensional probability densities |bb |2 and |sb |2 ,
for the isolated CHD2 T (left-hand side) and CHDT2 (right-hand side) after 800 fs of free evolution. At time 0 fs the wave
packets corresponded to a localized, chiral molecular structure (from [154]). See also text and figure A3.13.11.
along Qb1 occur along the x-axis, displacements along Qb2 are directed along the y-axis. One observes
a semiclassical, nearly periodic motion of the wave packet along the excited manifold with a period of
approximately 24 fs, corresponding to the frequency of the bending vibrations in the wave number region
around 1500 cm1 . At this stage of the excitation process, the motion of the wave packet is essentially
one-dimensional, as seen from the trajectory followed by the maximum of the probability distribution and
its practically unchanged shape during the oscillations back and forth between the turning points. The latter
lie on the potential energy section defined by the momentary energy E(t) of the wave packet, as described
above, and describe the classically accessible region in configuration space. These potential energy sections
are shown by the continuous curves in the figures, which are surrounded by dotted curves describing the
energy uncertainty.
The sequence on the right-hand side of figure A3.13.11 shows wave packets during the excitation along
the y-axis. Here, excitation was chosen to be antiparallel to the y-axis (E0 y ). This choice induces a
phase shift of between the two wave packets shown in the figure, in addition to forcing oscillations along
different directions. Excitation along the y-axis can be used to generate dynamically chiral structures. If the
excitation laser field is switched off, e.g. at time step 70 fs after beginning the excitation, the displacement of
the wave packet clearly corresponds to a bent molecular structure with angle 10 (e.g. in the xy plane
of figure A3.13.5). This structure will, of course, also change with time for the isolated molecule, and one
expects this change to be oscillatory, like a pendulum, at least initially. Clearly, IVR will play some role, if
not at this early stage, then at some later time. One question is, will it be CIVR or DIVR? When studying this
question with the isotopically substituted compounds CHD2 T and CHDT2 , the y-axis being perpendicular to
the Cs mirror plane, a bent CH chromophore corresponds to a chiral molecular structure with a well defined
chirality quantum number, say R. As time evolves, the wave packet moves to the other side of the symmetry
plane, Qb2 = 0, implying a change of chirality. In this context, the enantiomeric excess can be defined by the
probability
PR (t) =
(A3.13.69)
for right-handed (R) chiral structures (PL (t) = 1 PR (t) is the probability for left-handed (L) structures),
where
|b2 (t, Qb2 )|2 =
Qs
Qb1
(A3.13.70)
The time evolution of PR (t) is shown in figure A3.13.12 for the field free motion of wave packets for CHD2 T
and CHDT2 prepared by a preceding excitation along the y-axis.
In the main part of each figure, the evolution of PR calculated within the stretching and bending manifold
of states for the CH chromophore is shown (full curve). The dashed curve shows the evolution of PR within a
one-dimensional model, in which only the Qb2 bending manifold is considered during the dynamics. Within
this model there is obviously no IVR, and comparison of the full with the dashed curves helps to visualize the
effect of IVR. The insert on the left-hand side shows a survey of the evolution of PR for the one-dimensional
model during a longer time interval of 2 ps, while the insert on the right-hand side shows the evolution of
PR for the calculation within the full three-dimensional stretching and bending manifold of states during the
same time interval of 2 ps. The three-dimensional calculations yield a fast, initially nearly periodic, evolution,
with an approximate period of 20 fs, which is superimposed by a slower decay of probability corresponding
to an overall decay of enantiomeric excess |Dabs (t)| = |1 2PR (t)| on a time scale of 300400 fs for both
CHD2 T and CHDT2 . The decay is clearly more pronounced for CHD2 T (figure A3.13.12(a)). The first type
of evolution corresponds to a stereomutation reaction, while the second can be interpreted as racemization.
A further question is then related to the origin of this racemization.
Figure A3.13.14 shows the wave packet motion for CHD2 T and CHDT2 , roughly 800 fs after the
initially localized, chiral structure has been generated. Comparison with the wave packet motion allows for
Figure A3.13.14. Illustration of the quantum evolution (points) and Pauli master equation evolution (lines) in quantum
level structures with two levels (and 59 states each, left-hand side) and three levels (and 39 states each, right-hand side)
corresponding to a model of the energy shell IVR (horizontal transition in figure A3.13.1). From [38]. The two-level
structure (left) has two models: |Vij |2 = const and random signs (upper part), random Vij but Vm Vij Vm (lower
part). The right-hand side shows an evolution with initial diagonal density matrix (upper part) and a single trajectory
(lower part).
the conclusion that racemization is induced by the presence of DIVR between all vibrational modes of the
CH chromophore. However, while DIVR is quite complete for CHD2 T, after excitation along the y axis,
it is only two-dimensional for CHDT2 . A localized exchange of vibrational energy in terms of CIVR has
not been observed at any intermediate time step. Racemization is stronger for CHD2 T, for which DIVR
occurs in the full three-dimensional subspace of the CH chromophore, under the present conditions. It is less
pronounced for CHDT2 , which has a higher degree of localization of the wave packet motion. In comparison
with the one-dimensional calculations in figure A3.13.12, it becomes evident that there is a decay of the
overall enantiomeric excess for CHD2 T, as well as for CHDT2 , also in the absence of IVR. The decay takes
place on a time scale of 5001000 fs and is a consequence of the dephasing of the wave packet due to the
diagonal anharmonicity of the bending motion. This decay may, of course, also be interpreted as racemization.
However, it is much less complete than racemization in the three-dimensional case and clearly of secondary
importance for the enantiomeric decay in the first 200 fs.
A3.13.6 Statistical mechanical master equation treatment of intramolecular energy redistribution in
reactive molecules
The previous sections indicate that the full quantum dynamical treatment of IVR in an intermediate size
molecule even under conditions of coherent excitation shows phenomena reminiscent of relaxation and
Figure A3.13.15. Master equation model for IVR in highly excited C2 H6 . The left-hand side shows the quantum levels
of the reactive CC oscillator. The right-hand side shows the levels with a high density of states from the remaining 17
vibrational (and torsional) degrees of freedom (from [38]).
Figure A3.13.16. Illustration of the level populations (corresponding to the CC oscillator states) from various treatments in the model of figure A3.13.15 for C2 H6 at a total energy E = (hc) 41 000 cm1 and a threshold energy
E0 = (hc) 31 000 cm1 . The points are microcanonical equilibrium distributions. The crosses result from the solution
of the master equation for IVR at steady state and the lines are thermal populations at the temperatures indicated (from
[38]: quant. is calculated with quantum densities of states, class. with classical mechanical densities.).
equilibration. This suggests that, in general, at very high excitations in large polyatomic molecules with densities of states easily exceeding the order of 1010 cm1 (or about 109 molecular states in an energy interval corresponding to 1 J mol1 ), a statistical master equation treatment may be possible [38, 122]. Such an approach
has been justified by quantum simulations in model systems as well as analytical considerations [38], following early ideas in the derivation of the statistical mechanical Pauli equation [176]. Figure A3.13.14 shows the
kinetic behaviour in such model systems. The coarse grained populations of groups of quantum states (levels with less than 100 states, indexed by capital letters I and J ) at the same total energy show very similar behaviour if calculated from the Schrodinger equation, e.g. equation (A3.13.43), or the Pauli equation (A3.13.71),
p(t) = Y(t)p(0),
(A3.13.71)
Y(t) = exp(Kt),
(A3.13.72)
and the rate coefficient matrix elements in the limit of perturbation theory
KI J = 2 |VI J |2 /I .
(A3.13.73)
In equation (A3.13.73), I is the average angular frequency distance between quantum states within level I
and |VI J |2 is the average square coupling matrix element (as angular frequency) between the quantum states
in levels I and J (of total number of states NI and NJ , respectively) and is given by:
|VI J |2 =
1 1
N I NJ
NJ
NI
|Vij |2 .
(A3.13.74)
i=1 j =1
Figure A3.13.14 seems to indicate that the Pauli equation is a strikingly good approximation for treating
IVR under these conditions, involving even relatively few quantum states. This is, however, only true in
this simple manner because we assume in the model that all the couplings are randomly distributed around
their typical values. This excludes any symmetry selection rules for couplings within the set of quantum
states considered [177]. More generally, one has to consider only sets of quantum states with the same set of
good (conserved) quantum numbers in such a master equation treatment. It is now well established that even
in complex forming collisions leading to maximum energy transfer by IVR (section A3.13.3.3), conserved
quantum numbers such as nuclear spin symmetry and parity lead to considerable restrictions [177, 178]. More
generally, one has to identify approximate symmetries on short time scales, which lead to further restrictions
on the density of strongly coupled states [179]. Thus, the validity of a statistical master equation treatment
for IVR in large polyatomic molecules is not obvious a priori and has to be established individually for at
least classes of molecular systems, if not on a case by case basis.
Figure A3.13.15 shows a scheme for such a Pauli equation treatment of energy transfer in highly excited
ethane, e.g. equation (A3.13.75), formed at energies above both thresholds for dissociation in chemical
activation:
H + C2 H5 C2 H6 2CH3 .
(A3.13.75)
The figure shows the migration of energy between excited levels of the ultimately reactive CC oscillator, the
total energy being constant at E/ hc = 41 000 cm1 with a CC dissociation threshold of 31 000 cm1 . The
energy balance is thus given by:
17
Etot = ECC +
Ei .
(A3.13.76)
i=1
The microcanonical equilibrium distributions are governed by the densities s1 in the (s 1) = 17 oscillators
(figure A3.13.15):
(n)
pmicro (n) = s1
(k)
s1
(A3.13.77)
where the 17 remaining degrees of freedom of ethane form essentially a heat bath. The kinetic master equation treatment of this model leads to steady-state populations shown in figure A3.13.16. This illustrates that the
steady-state populations under conditions where reaction equation (A3.13.75) competes with IVR differ from
the microcanonical equilibrium populations at high energy, and both differ from thermal distributions shown
as lines (quantum or classical). Whereas the deviation from a thermal distribution is well understood and
handled by standard statistical theories such as RRKM (chapter A3.12) and the statistical adiabatic channel
model [76], the deviation from the microcanonical distribution would lead to an intramolecular nonequilibrium
effect on the rates of reaction which so far has not been well investigated experimentally [3739].
A3.13.7
It has been understood for more than a century that energy redistribution is a key process in chemical reactions,
including in particular the oldest process of chemical technology used by mankind: fire or combustion, where
both radiative and collisional processes are relevant. Thus one might think that this field has reached a stage
of maturity and saturation. Nothing could be further from the truth. While collisional energy transfer is now
often treated in reaction systems in some detail, as is to some extent routine in unimolecular reactions, there
remain plenty of experimental and theoretical challenges. In the master equation treatments, which certainly
should be valid here, one considers a statistical, macroscopic reaction system consisting of reactive molecules
in a mixture, perhaps an inert gas heat bath.
The understanding of the second process considered in this chapter, intramolecular energy redistribution
within a single molecular reaction system, is still in its infancy. It is closely related to the challenge of
finding possible schemes to control the dynamics of atoms in molecules and the related change of molecular
structure during the course of a chemical reaction [10, 117, 154, 175], typically in the femtosecond time scale,
which has received increasing attention in the last few decades [180182]. The border between fully quantum
dynamical treatments, classical mechanical theories and, finally, statistical master equations for IVR type
processes needs to be explored further experimentally and theoretically in the future. Unravelling details of
the competition between energy redistribution and reaction in individual molecules remains an important task
for the coming decades [3740].
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
[25]
[26]
[27]
[28]
[29]
[30]
[31]
[32]
[33]
[34]
[35]
[36]
[37]
[38]
[39]
[40]
[41]
[42]
[43]
[44]
[45]
[46]
[47]
[48]
[49]
[50]
[51]
[52]
[53]
[54]
[55]
[56]
[57]
[58]
Pritchard H O 1975 Reaction Kinetics vol 1, ed P G Ashmore (London: The Chemical Society)
Quack M and Troe J 1981 Current aspects of unimolecular reactions Int. Rev. Phys. Chem. 1 97147
Golden D M and Benson S W 1975 Physical Chemistry. An Advanced Treatise vol VII (New York: Academic) p 57
Tardy D C and Rabinovitch B S 1977 Intermolecular vibrational energy transfer in thermal unimolecular systems Chem. Rev. 77
369408
Troe J 1978 Atom and radical recombination reactions Ann. Rev. Phys. Chem. 29 22350
Hippler H and Troe J 1989 Advances in Gas Phase Photochemistry and Kinetics ed M N R Ashfold and J E Baggott (London:
Royal Society of Chemistry) pp 20962
Kraijnovitch D J, Parmenter C S and Catlett D L Jr 1987 State-to-state vibrational transfer in atom-molecule collisions. Beams
vs. bulbs Chem. Rev. 87 23788
Gilbert R G and Smith S C 1990 Theory of Unimolecular and Recombination Reactions (London: Blackwell)
Lambert J D 1977 Vibrational and Rotational Relaxation in Gases (Oxford: Oxford University Press)
Weitz E and Flynn G W 1981 Vibrational energy flow in the ground electronic states of polyatomic molecules Adv. Chem. Phys.
47 185235
Oref I and Tardy D C 1990 Energy transfer in highly excited large polyatomic molecules Chem. Rev. 90 140745
Weston R E and Flynn G W 1992 Relaxation of molecules with chemically significant amounts of vibrational energy: the dawn
of the quantum state resolved era Ann. Rev. Phys. Chem. 43 55989
Howard M J and Smith I W M 1983 The kinetics of radical-radical processes in the gas phase Prog. Reaction Kin. 12 57200
Orr B J and Smith I W M 1987 Collision-induced vibrational energy transfer in small polyatomic molecules J. Phys. Chem. 91
610619
Flynn G W, Parmenter C S and Wodtke A M 1996 Vibrational energy transfer J. Phys. Chem. 100 12 81738
Forster Th 1948 Zwischenmolekulare Energiewanderung und Fluoreszenz Ann. Phys. 2 5575
Juzeliunas G and Andrews D L 2000 Quantum electrodynamics of resonance energy transfer Adv. Chem. Phys. 112 357410
Quack M 1982 Reaction dynamics and statistical mechanics of the preparation of highly excited states by intense infrared radiation
Adv. Chem. Phys. 50 395473
Jortner J, Rice S A and Hochstrasser R M 1969 Radiationless transitions in photochemistry Adv. Photochem. 7 149
Quack M and Kutzelnigg W 1995 Molecular spectroscopy and molecular dynamics: theory and experiment Ber. Bunsenges. Phys.
Chem. 99 23145
Quack M 1981 Statistical mechanics and dynamics of molecular fragmentation Nuovo Cimento B 63 35877
Quack M 1995 Molecular femtosecond quantum dynamics between less than yoctoseconds and more than days: experiment and
theory Femtosecond Chemistry ed J Manz and L Woeste (Weinheim: Verlag Chemie) pp 781818
Oppenheim I, Shuler K E and Weiss G H 1977 Stochastic Processes in Chemical Physics, The Master Equation (Cambridge, MA:
MIT Press)
van Kampen N G 1981 Stochastic Processes in Physics and Chemistry (Amsterdam: North-Holland)
Gear C W 1971 Numerical Initial Value Problems in Ordinary Differential Equations (Englewood Cliffs, NJ: Prentice-Hall)
Shampine S 1994 Numerical Solutions of Ordinary Differential Equations (New York: Chapman and Hall)
Troe J 1977 Theory of thermal unimolecular reactions at low pressures. I. Solutions of the master equation J. Chem. Phys. 66
474557
Troe J 1977 Theory of thermal unimolecular reactions at low pressures. II. Strong collision rate constants. Applications J. Chem.
Phys. 66 4758
Troe J 1983 Theory of thermal unimolecular reactions in the fall-off range. I. Strong collision rate constants Ber. Bunsenges. Phys.
Chem. 87 1619
Quack M 1979 Master equations for photochemistry with intense infrared light Ber. Bunsenges. Phys. Chem. 83 75775
Dove J E, Nip W and Teitelbaum H 1975 Proc. XVth Int. Symp. on Combustion (The Combustion Institute) p 903
Olschewski H A, Troe J and Wagner H G 1966 Niederdruckbereich und Hochdruckbereich des unimolekularen N2 O-Zerfalls Ber.
Bunsenges. Phys. Chem. 70 450
Martinengo A, Troe J and Wagner H G 1966 Z. Phys. Chem. (Frankfurt) 51 104
Johnston H S 1951 Interpretation of the data on the thermal decomposition of nitrous oxide J. Chem. Phys. 19 6637
Venkatesh P K, Dean A M, Cohen M H and Carr R W 1999 Master equation analysis of intermolecular energy transfer in multiplewell, multiple-channel unimolecular reactions. II. Numerical methods and application to the mechanism of the C2 H5 + O2
reaction J. Chem. Phys. 111 8313
Smith K and Thomson R M 1978 Computer Modelling of Gas Lasers (New York: Plenum)
Hirschfelder J D, Curtiss C F and Bird R B 1964 Molecular Theory of Gases and Liquids (New York: Wiley)
Tabor M, Levine R D, Ben-Shaul A and Steinfeld J I 1979 Microscopic and macroscopic analysis of non-linear master equations:
vibrational relaxation of diatomic molecules Mol. Phys. 37 14158
Treanor C E, Rich J W and Rehm R G 1968 Vibrational relaxation of anharmonic oscillators with exchange-dominated collisions
J. Chem. Phys. 48 1798807
McCaffery A J 1999 Quasiresonant vibrationrotation transfer: a kinematic interpretation J. Chem. Phys. 111 7697
Levine R D and Bernstein R B 1987 Molecular Reaction Dynamics and Chemical Reactivity (New York: Oxford University
Press)
[59] Steinfeld J I and Klemperer W 1965 Energy-transfer processes in monochromatically excited iodine molecules. I. Experimental
results J. Chem. Phys. 42 347597
[60] Gianturco F A 1979 The Transfer of Molecular Energies by Collision (Heidelberg: Springer)
[61] Bowman J M (ed) 1983 Molecular Collision Dynamics (Berlin: Springer)
[62] Hutson J M and Green S 1994 MOLSCAT computer code, version 14, distributed by Collaborative Computational Project No 6
of the Engineering and Physical Sciences Research Council (UK)
[63] Alexander M H and Manolopoulos D E 1987 A stable linear reference potential algorithm for solution of the quantum close-coupled
equations in molecular scattering theory J. Chem. Phys. 86 204450
[64] Bodo E, Gianturco F A and Paesani F 2000 Testing intermolecular potentials with scattering experiments: HeCO rotationally
inelastic collisions Z. Phys. Chem., NF 214 101334
[65] Fluendy M A D and Lawley K P 1973 Applications of Molecular Beam Scattering (London: Chapman and Hall)
[66] Faubel M and Toennies J P 1977 Scattering studies of rotational and vibrational excitation of molecules Adv. Atom. Mol. Phys.
13 229
[67] Faubel M 1983 Vibrational and rotational excitation in molecular collisions Adv. Atom. Mol. Phys. 19 345
[68] Bunker D L 1971 Methods in Computational Physics vol 10, ed B Alder (New York: Academic)
[69] Lenzer T, Luther K, Troe J, Gilbert R G and Lim K F 1995 Trajectory simulations of collisional energy transfer in highly excited
benzene and hexafluorobenzene J. Chem. Phys. 103 62641
[70] Grigoleit U, Lenzer T and Luther K 2000 Temperature dependence of collisional energy transfer in highly excited aromatics
studied by classical trajectory calculations Z. Phys. Chem., NF 214 106585
[71] Barker J R 1984 Direct measurement of energy transfer in rotating large molecules in the electronic ground state J. Chem. Phys.
88 11
[72] Miller L A and Barker J R 1996 Collisional deactivation of highly vibrationally excited pyrazine J. Chem. Phys. 105 138391
[73] Hippler H, Troe J and Wendelken H J 1983 Collisional deactivation of vibrationally highly excited polyatomic molecules. II. Direct
observations for excited toluene J. Chem. Phys. 78 6709
[74] Hold U, Lenzer T, Luther K, Reihs K and Symonds A C 2000 Collisional energy transfer probabilities of highly excited molecules
from kinetically controlled selective ionization (KCSI). I. The KCSI technique: experimental approach for the determination
of P (E , E) in the quasicontinuous energy range J. Chem. Phys. 112 407689
[75] Steinfeld J I, Ruttenberg P, Millot G, Fanjoux G and Lavorel B 1991 Scaling laws for inelastic collision processes in diatomic
molecules J. Phys. Chem. 95 963847
[76] Quack M and Troe J 1974 Specific rate constants of unimolecular processes II. Adiabatic channel model Ber. Bunsenges. Phys.
Chem. 78 24052
[77] Quack M and Troe J 1998 Statistical adiabatic channel model Encyclopedia of Computational Chemistry vol 4, ed P von Rague
Schleyer et al (New York: Wiley) pp 270826
[78] Quack M and Troe J 1975 Complex formation in reactive and inelastic scattering: statistical adiabatic channel model of unimolecular processes III Ber. Bunsenges. Phys. Chem. 79 17083
[79] Quack M 1979 Quantitative comparison between detailed (state selected) relative rate data and averaged (thermal) absolute rate
data for complex forming reactions J. Phys. Chem. 83 1508
[80] Clary D C, Gilbert R G, Bernshtein V and Oref I 1995 Mechanisms for super collisions Faraday Discuss. Chem. Soc. 102
42333
[81] Marquardt R, Quack M, Stohner J and Sutcliffe E 1986 Quantum-mechanical wavepacket dynamics of the CH group in the
symmetric top X3 CH compounds using effective Hamiltonians from high-resolution spectroscopy J. Chem. Soc., Faraday
Trans. 2 82 117387
[82] Herzberg G 1966 Molecular Spectra and Molecular Structure III. Electronic Spectra and Electronic Structure of Polyatomic
Molecules (New York: Van Nostrand-Reinhold) (reprinted in 1991)
[83] Rice S A 1981 An overview of the dynamics of intramolecular transfer of vibrational energy Adv. Chem. Phys. 47 117200
[84] Beil A, Luckhaus D, Quack M and Stohner J 1997 Intramolecular vibrational redistribution and unimolecular reactions: concepts
and new results on the femtosecond dynamics and statistics in CHBrClF Ber. Bunsenges. Phys. Chem. 101 31128
[85] Quack M 1993 Molecular quantum dynamics from high resolution spectroscopy and laser chemistry J. Mol. Struct. 292 17195
[86] Heller E J 1975 Time-dependent approach to semiclassical dynamics J. Chem. Phys. 62 154455
[87] Heller E J 1981 The semiclassical way to molecular spectroscopy Acc. Chem. Res. 14 36878
[88] Heller E J 1983 The correspondence principle and intramolecular dynamics Faraday Discuss. Chem. Soc. 75 14153
[89] Noid D W, Koszykowski M L and Marcus R A 1981 Quasiperiodic and stochastic behaviour in molecules Ann. Rev. Phys. Chem.
32 267309
[90] Marcus R A 1983 On the theory of intramolecular energy transfer Faraday Discuss. Chem. Soc. 75 10315
[91] Hose G and Taylor H S 1982 A quantum analog to the classical quasiperiodic motion J. Chem. Phys. 76 535664
[92] Wyatt R E, Hose G and Taylor H S 1983 Mode-selective multiphoton excitation in a model system Phys. Rev. A 28 81528
[93] Heather R and Metiu H 1985 Some remarks concerning the propagation of a Gaussian wave packet trapped in a Morse potential
Chem. Phys. Lett. 118 55863
[94] Sawada S and Metiu H 1986 A multiple trajectory theory for curve crossing problems obtained by using a Gaussian wave packet
representation of the nuclear motion J. Chem. Phys. 84 22738
[95] Miller W H 1974 Classical-limit quantum mechanics and the theory of molecular collisions Adv. Chem. Phys. 25 69177
[96] van Gunsteren W F and Berendsen H J C 1990 Computer simulation of molecular dynamics: methodology, applications, and
perspectives in chemistry Angew. Chem. Int. Ed. Engl. 29 9921023
[97] Marquardt R and Quack M 1991 The wave packet motion and intramolecular vibrational redistribution in CHX3 molecules under
infrared multiphoton excitation J. Chem. Phys. 95 485467
[98] Dubal H-R and Quack M 1980 Spectral bandshape and intensity of the CH chromophore in the infrared spectra of CF3 H and
C4 F9 H Chem. Phys. Lett. 72 3427
Dubal H-R and Quack M 1981 High resolution spectroscopy of fluoroform Chem. Phys. Lett. 80 43944
[99] Dubal H-R and Quack M 1984 Tridiagonal Fermi resonance structure in the IR spectrum of the excited CH chromophore in CF3 H
J. Chem. Phys. 81 377991
[100] Quack M 1990 Spectra and dynamics of coupled vibrations in polyatomic molecules Ann. Rev. Phys. Chem. 41 83974
[101] Maynard A T, Wyatt R E and Iung C 1995 A quantum dynamical study of CH overtones in fluoroform. I. A nine-dimensional
ab initio surface, vibrational spectra and dynamics J. Chem. Phys. 103 837290
[102] Maynard A T, Wyatt R E and Iung C 1997 A quantum dynamical study of CH overtones in fluoroform. II. Eigenstates of the
vCH = 1 and vCH = 2 regions J. Chem. Phys. 106 948396
[103] Wyatt R E, Iung C and Leforestier C 1992 Quantum dynamics of overtone relaxation in benzene. II. Sixteen-mode model for
relaxation from CH(v = 3) J. Chem. Phys. 97 347786
[104] Minehardt T A, Adcock J D and Wyatt R E 1999 Quantum dynamics of overtone relaxation in 30-mode benzene: a time-dependent
local mode analysis for CH(v = 2) J. Chem. Phys. 110 332634
[105] Gatti F, Iung C, Leforestier C and Chapuisat X 1999 Fully coupled 6D calculations of the ammonia vibrationinversiontunneling
states with a split Hamiltonian pseudospectral approach J. Chem. Phys. 111 723643
[106] Luckhaus D 2000 6D vibrational quantum dynamics: generalized coordinate discrete variable representation and (a)diabatic
contraction J. Chem. Phys. 113 132947
[107] Fehrensen B, Luckhaus D and Quack M 1999 Mode selective stereomutation tunnelling in hydrogen peroxide isotopomers Chem.
Phys. Lett. 300 31220
[108] Fehrensen B, Luckhaus D and Quack M 1999 Inversion tunneling in aniline from high resolution infrared spectroscopy and an
adiabatic reaction path Hamiltonian approach Z. Phys. Chem., NF 209 119
[109] Zhang D H, Wu Q, Zhang J Z H, von Dirke M and Bacic Z 1995 Exact full dimensional bound state calculations for (HF)2 , (DF)2
and HFDF J. Chem. Phys. 102 231525
[110] Quack M and Suhm M A 1998 Spectroscopy and quantum dynamics of hydrogen fluoride clusters Advances in Molecular
Vibrations and Collision Dynamics, Vol. III Molecular Clusters ed J Bowman and Z Bacic (JAI Press) pp 20548
[111] Qiu Y and Bacic Z 1998 Vibrationrotationtunneling dynamics of (HF)2 and (HCl)2 from full-dimensional quantum bound
state calculations Advances in Molecular Vibrations and Collision Dynamics, Vol. III Molecular Clusters ed J Bowman and
Z Bacic (JAI Press) pp 183204
[112] Loesch H J and Remscheid A 1990 Brute force in molecular reaction dynamics: a novel technique for measuring steric effects
J. Chem. Phys. 93 477990
[113] Seideman T 1995 Rotational excitation and molecular alignment in intense laser fields J. Chem. Phys. 103 788796
[114] Friedrich B and Herschbach D 1995 Alignment and trapping of molecules in intense laser fields Phys. Rev. Lett. 74 46236
[115] Kim W and Felker P M 1996 Spectroscopy of pendular states in optical-field-aligned species J. Chem. Phys. 104 114750
[116] Quack M and Sutcliffe E 1983 Quantum interference in the IR-multiphoton excitation of small asymmetric-top molecules: ozone
Chem. Phys. Lett. 99 16772
[117] Quack M and Sutcliffe E 1984 The possibility of mode-selective IR-multiphoton excitation of ozone Chem. Phys. Lett. 105 14752
[118] Kosloff R 1994 Propagation methods for quantum molecular dynamics Ann. Rev. Phys. Chem 45 14578
[119] Dey B D, Askar A and Rabitz H 1998 Multidimensional wave packet dynamics within the fluid dynamical formulation of the
Schrodinger equation J. Chem. Phys. 109 877082
[120] Quack M 1992 Time dependent intramolecular quantum dynamics from high resolution spectroscopy and laser chemistry Time
Dependent Quantum Molecular Dynamics: Experiment and Theory. Proc. NATO ARW 019/92 (NATO ASI Ser. Vol 299)
ed J Broeckhove and L Lathouwers (New York: Plenum) pp 293310
[121] Quack M 1981 Faraday Discuss. Chem. Soc. 71 30911, 3256, 35964 (Discussion contributions on flexible transition states and
vibrationally adiabatic models; statistical models in laser chemistry and spectroscopy; normal, local, and global vibrational
states)
[122] Quack M 1982 The role of intramolecular coupling and relaxation in IR-photochemistry Intramolecular Dynamics, Proc. 15th
Jerusalem Symp. on Quantum Chemistry and Biochemistry (Jerusalem, Israel, 29 March1 April 1982) ed J Jortner and
B Pullman (Dordrecht: Reidel) pp 37190
[123] von Puttkamer K, Dubal H-R and Quack M 1983 Time-dependent processes in polyatomic molecules during and after intense
infrared irradiation Faraday Discuss. Chem. Soc. 75 197210
[124] von Puttkamer K, Dubal H R and Quack M 1983 Temperature-dependent infrared band structure and dynamics of the CH
chromophore in C4 F9 CCH Chem. Phys. Lett. 45 35862
[125] Segall J, Zare R N, Dubal H R, Lewerenz M and Quack M 1987 Tridiagonal Fermi resonance structure in the vibrational spectrum
of the CH chromophore in CHF3 . II. Visible spectra J. Chem. Phys. 86 63446
[126] Boyarkin O V and Rizzo T R 1996 Secondary time scales of intramolecular vibrational energy redistribution in CF3 H studied by
vibrational overtone spectroscopy J. Chem. Phys. 105 628592
[127] Schulz P A, Sudbo A S, Kraijnovitch D R, Kwok H S, Shen Y R and Lee Y T 1979 Multiphoton dissociation of polyatomic
molecules Ann. Rev. Phys. Chem. 30 395409
[128] Zewail A H 1980 Laser selective chemistryis it possible? Phys. Today Nov, 2733
[129] Quack M 1978 Theory of unimolecular reactions induced by monochromatic infrared radiation J. Chem. Phys. 69
1282307
[130] Quack M, Stohner J and Sutcliffe E 1985 Time-dependent quantum dynamics of the picosecond vibrational IR-excitation of polyatomic molecules Time-Resolved Vibrational Spectroscopy, Proc. 2nd Int. Conf. Emil-Warburg Symp. (Bayreuth-Bischofsgrun,
Germany, 37 June 1985) ed A Laubereau and M Stockburger (Berlin: Springer) pp 2848
[131] Mukamel S and Shan K 1985 On the selective elimination of intramolecular vibrational redistribution using strong resonant laser
fields Chem. Phys. Lett. 5 48994
[132] Lupo D W and Quack M 1987 IR-laser photochemistry Chem. Rev. 87 181216
[133] von Puttkamer K and Quack M 1989 Vibrational spectra of (HF)2 , (HF)n and their D-isotopomers: mode selective rearrangements
and nonstatistical unimolecular decay Chem. Phys. 139 3153
[134] Quack M 1991 Mode selective vibrational redistribution and unimolecular reactions during and after IR-laser excitation Mode
Selective Chemistry ed J Jortner, R D Levine and B Pullman (Dordrecht: Kluwer) pp 4765
[135] Crim F F 1993 Vibrationally mediated photodissociation: exploring excited state surfaces and controlling decomposition pathways
Ann. Rev. Phys. Chem. 44 397428
[136] Nesbitt D J and Field R W 1996 Vibrational energy flow in highly excited molecules: role of intramolecular vibrational redistribution J. Phys. Chem. 100 12 73556
[137] He Y, Pochert J, Quack M, Ranz R and Seyfang G 1995 Discussion contributions on unimolecular reactions dynamics J. Chem.
Soc. Faraday Discuss. 102 35862, 3725
[138] Siegman A E 1986 Lasers (Oxford: Oxford University Press)
[139] Quack M and Sutcliffe E 1986 Program 515. URIMIR: unimolecular reactions induced by monochromatic infrared radiation
QCPE Bull. 6 98
[140] Marquardt R, Quack M and Stohner J, at press
[141] Marquardt R and Quack M 1996 Radiative excitation of the harmonic oscillator with applications to stereomutation in chiral
molecules Z. Phys. D 36 22937
[142] Cotting R, Huber J R and Engel V 1993 Interference effects in the photodissociation of FNO J. Chem. Phys. 100 10408
[143] Schinke R and Huber J R 1995 Molecular dynamics in excited electronic statestime-dependent wave packet studies Femtosecond
Chemistry: Proc. Berlin Conf. Femtosecond Chemistry (Berlin, March 1993) (Weinheim: Verlag Chemie)
[144] Schinke R and Huber J R 1993 Photodissociation dynamics of polyatomic molecules. The relationship between potential energy
surfaces and the breaking of molecular bonds J. Phys. Chem. 97 3463
[145] Meier C and Engel V 1995 Pumpprobe ionization spectroscopy of a diatomic molecule: sodium molecule as a prototype example
Femtosecond Chemistry: Proc. Berlin Conf. Femtosecond Chemistry (Berlin, March 1993) (Weinheim: Verlag Chemie)
[146] Meyer S and Engel V 1997 Vibrational revivals and the control of photochemical reactions J. Phys. Chem. 101 774953
[147] Flothmann H, Beck C, Schinke R, Woywod C and Domcke W 1997 Photodissociation of ozone in the Chappuis band. II. Timedependent wave packet calculations and interpretation of diffuse vibrational structures J. Chem. Phys. 107 7296313
[148] Loettgers A, Untch A, Keller H-M, Schinke R, Werner H-J, Bauer C and Rosmus P 1997 Ab initio study of the photodissociation
of HCO in the first absorption band: three-dimensional wave packet calculations including the X 2 A A 2 A RennerTeller
coupling J. Chem. Phys. 106 3186204
[149] Keller H-M and Schinke R 1999 The unimolecular dissociation of HCO. IV. Variational calculation of Siegert states J. Chem.
Phys. 110 988797
[150] Braun M, Metiu H and Engel V 1998 Molecular femtosecond excitation described within the Gaussian wave packet approximation
J. Chem. Phys. 108 89838
[151] Dubal H-R, Ha T-K, Lewerenz M and Quack M 1989 Vibrational spectrum, dipole moment function, and potential energy surface
of the CH chromophore in CHX3 molecules J. Chem. Phys. 91 6698713
[152] Lewerenz M and Quack M 1988 Vibrational spectrum and potential energy surface of the CH chromophore in CHD3 J. Chem.
Phys. 88 540832
[153] Marquardt R, Sanches Goncalves N and Sala O 1995 Overtone spectrum of the CH chromophore in CHI3 J. Chem. Phys. 103
8391403
[154] Marquardt R, Quack M and Thanopoulos I 2000 Dynamical chirality and the quantum dynamics of bending vibrations of the CH
chromophore in methane isotopomers J. Phys. Chem. A 104 612949
[155] Ha T-K, Lewerenz M, Marquardt R and Quack M 1990 Overtone intensities and dipole moment surfaces for the isolated CH
chromophore in CHD3 and CHF3 : experiment and ab initio theory J. Chem. Phys. 93 7097109
[156] Hollenstein H, Marquardt R, Quack M and Suhm M A 1994 Dipole moment function and equilibrium structure of methane in an
analytical, anharmonic nine-dimensional potential surface related to experimental rotational constants and transition moments
by quantum Monte Carlo calculations J. Chem. Phys. 101 3588602
[158] Kerner E H 1958 Note on the forced and damped oscillator in quantum mechanics Can. J. Phys. 36 3717
[159] Marquardt R and Quack M 1989 Infrared-multiphoton excitation and wave packet motion of the harmonic and anharmonic
oscillators: exact solutions and quasiresonant approximation J. Chem. Phys. 90 63207
[160] Marquardt R and Quack M 1989 Molecular motion under the influence of a coherent infrared-laser field Infrared Phys. 29 485501
[161] Rice O K and Ramsperger H C 1927 Theories of unimolecular gas reactions at low pressures J. Am. Chem. Soc. 49 161729
[162] Kassel L S 1928 Studies in homogeneous gas reactions I J. Phys. Chem. 32 22542
[163] Marcus R A and Rice O K 1951 The kinetics of the recombination of methyl radicals and iodine atoms J. Phys. Colloid. Chem.
55 894908
[164] Evans M G and Polanyi M 1935 Some applications of the transition state method to the calculation of reaction velocities, especially
in solution Trans. Faraday Soc. 31 87594
[165] Eyring H 1935 The activated complex in chemical reactions J. Chem. Phys. 3 10715
[166] Hofacker L 1963 Quantentheorie chemischer Reaktionen Z. Naturf. A 18 60719
[167] Robinson P J and Holbrook K A 1972 Unimolecular Reactions (New York: Wiley)
[168] Quack M and Troe J 1981 Statistical methods in scattering Theor. Chem. Adv. Perspect. B 6 199276
[169] Truhlar D G, Garrett B C and Klippenstein S J 1996 Current status of transition state theory J. Phys. Chem. 100 12 771800
[170] Baer T and Hase W L 1996 Unimolecular Reaction Dynamics. Theory and Experiment (New York: Oxford University Press)
[171] Holbrook K A, Pilling M J and Robertson S H 1996 Unimolecular Reactions 2nd edn (New York: Wiley)
[172] Quack M 1990 The role of quantum intramolecular dynamics in unimolecular reactions Phil. Trans. R. Soc. Lond. A 332 20320
[173] Luckhaus D and Quack M 1993 The role of potential anisotropy in the dynamics of the CH chromophore in CHX3 (C3v ) symmetric
tops Chem. Phys. Lett. 205 27784
[174] Quack M 1989 Structure and dynamics of chiral molecules Angew. Chem. Int. Ed. Engl. 28 57186
[175] Herve S, Le Quere F and Marquardt R 2001 Rotational and vibrational wave packet motion during the IR multiphoton excitation
of HF J. Chem. Phys. 114 82635
Further Reading
Ashmore P G and Donovan R J (ed) 1980 Specialists Periodical Report: Gas Kinetics and Energy Transfer vol 1 (1975),
vol 2 (1977), vol 3 (1978), vol 4 (1980) (London: The Royal Society of Chemistry)
Bunsen. Discussion on Molecular spectroscopy and molecular dynamics. Theory and experiment Ber. Bunsengesellschaft
Phys. Chem. 99 231582
Bunsen. Discussion on Intramolecular processes Ber. Bunsenges. Phys. Chem. 92 209450
Bunsen. Discussion on Unimolecular reactions Ber. Bunsenges. Phys. Chem. 101 304635
Faraday Discuss. Chem. Soc. 1983 Intramolecular kinetics, No 75
Faraday Discuss. Chem. Soc. 1986 Dynamics of molecular photofragmentation, No 82
Faraday Discuss. Chem. Soc. 1995 Unimolecular dynamics, No 112
Gilbert R G and Smith S C 1990 Theory of Unimolecular and Recombination Reactions (Oxford: Blackwell)
Holbrook K, Pilling M J and Robertson S H 1996 Unimolecular Reactions (New York: Wiley)
Levine R D and Bernstein R B 1987 Molecular Reaction Dynamics and Chemical Reactivity (New York: Oxford University
Press)
Quack M 1982 Adv. Chem. Phys. 50 395473
Quack M and Troe J 1981 Statistical methods in scattering Theor. Chem.: Adv. Perspect. B 6 199276