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H. MEYER
1. Introduction
Solid hydrogen is a remarkable medium where the angular
momentum J of the ortho-Hz impurities in para Hz can diffuse
through the lattice (1). It is now almost 20 years since this
phenomenon was discovered, and therefore it seems appropriate
to present a review on the status of knowledge on this
intriguing topic and to suggest further research.
The quantum diffusion rate is too slow to be observed
directly. This is to be contrasted with classical diffusion, which
above a minimum hopping frequency, v, from one site to a
neighboring one, can be detected by nuclear magnetic resonance (nmr) techniques such as rotating-frame pulse sequences
(see ref. 2 and references cited therein) or with pulsed magnetic
field gradients. Instead, quantum diffusion in Hz is detected via
the clustering (or unclustering) of the diffusing excitations as a
function of time after a rapid change in temperature. This
redistribution results from the anisotropic electric quadmpolequadmpole (EQQ) interaction between the 0-H2 particles,
leading to changes with temperature in the equilibrium proportions of the clusters of various sizes. Hence the motion of the
excitations permits the free energy F to be minimized. At any
temperature there is such motion, and at equilibrium, on
average as many pairs are formed as are broken up. For kBT >>
A E , the energy released through formation of a nearest
neighboring pair or larger 0-H2 cluster, the distribution is
random. As will be shown later, A E / k B = 3 K . As T is
decreased, the proportion of pairs and larger clusters in
equilibrium increases, and conversely as the temperature
increases, the distribution becomes more randomized.
Classical thermally activated diffusion in Hz can be expressed
by the average time T~ between successive jumps from one site
to another. This time, obtained from nmr relaxation measurements (see ref. 3 and refs. therein to earlier work), is given by
T! 5
random, but as T decreases below 7 K, this diffusion mechanism becomes too slow to permit rearrangement of the o-Hz
particles in an acceptable time, say a few hours. Hence other
mechanisms based on quantum effects have to be invoked to
account for the observed diffusion below 4 K.
The original technique leading to the accidental discovery of
this motion was continuous-wave proton nmr (4). Here, the
characteristic spectrum intensity of the isolated o-Hz impurities,
henceforth called "singles," is found to decrease with time after
a rapid lowering of the temperature. Nuclear magnetic resonance
in hexagonal close-packed (hcp) H, single crystals makes it
possible, in fact, to monitor the spectrum intensity, and hence
the density of the singles and of nearest neighboring (nn) 0-HZ
pairs. Of the latter there are two kinds: the "in-plane" (IP) and
the "out-of-plane" (OP) pairs having their axis in and out of the
basal plane. Hence, one can check whether or not a decrease of
one species, the singles for instance, happens simultaneously
with an increase of pairs ( 5 ) .
After the first observations, other methods led to the detection
of quantum diffusion. The thermodynamic methods (6, 7)
exploit the dependence of the free energy, F, of the solid on the
statistical distribution of o-H, in the lattice. This potential can
be calculated in terms of the EQQ interaction between the o-H,
molecules. For small clusters of three and less, the energy states
have been calculated (8).' Derivatives of F, namely, the
specific heat, Cv,and the pressure, Pv,at,constant volume then
show a time dependence during the clustering (9). The optical
methods (10-12) are based on the time dependence of the
transition intensity between the energy states of the pairs.
Therefore, just like the nmr spectra, they measure the change
with time in the population of pairs.
A further method of clustering detection is the thermal
conductivity (13), which is a sensitive measure of phononscattering processes, and it is affected by the cluster sizes.
'See also A. B. Harris, unpublished results. 1968.
1454
&
[3]
WQ
= 2.5
x 10" ( r / k B ) X1I2radvs-l,
(Gaussian)
v = 1.3 X
[7]
v = 1 . 2 x I O - ~ X - ~s ' ~
For X = 1
X-I'z
(Gaussian)
(statistical)
1455
MEYER
= ( 1 2 ~ ) and
~ ' one has TC = 700 s (Gaussian) and TC = 32 s
(statistical).
The same calculation of the resonant ortho-para conversion
frequency vo of an isolated ( J = 1) p-D2 impurity in ( J = 0)
o-D2 has been carried out by Van Kranendonk (1). Here the
nuclear spins are I = 1 for ( J = 1)D2 and I = 0 and 2 for
,
into an expression
( J = O)D2. The nuclear g factor, y ~entering
similar to [I], is only O.15yP, and it is chiefly responsible for the
much smaller jump frequency in D2 (v (D2) = 5 X l o p 3 v
(Hz)). This implies that the redistribution times of ( J = 1)D2
impurities would be about two orders of magnitude larger than
in Hz and thus not observable on a realistic experimental time
scale.
On a macroscopic scale, one can describe (6) the particleredistribution process by a rate equation, where for simplicity
only singles and pairs are included and larger clusters are
neglected. The single $ pair rate equation is then
where s = N,/N is the fraction of singles and where the terms on
the right-hand side refer, respectively, to the formation and
breaking up of pairs. Here the reaction parameters A and B are
taken to be functions of the average (time independent)
composition and the temperature. The solution of this equation
can be written as
[9]
s - s, =
= 0.05 x-'I3 v-
(DM)
= 3.8 X
lo3 x-'I6s ,
(DM, Gaussian)
(KM)
1456
= 4.2
[15]
x lo4 X s,
(DM, stat.)
9.9 x 1 0 ' ~ S,
~ ' ~ (KM, stat.)
Gaussian
17
quantum
tunneling
diffusion model
vcc~-112v< y;Kx-213~-'
rv\
v -kinet~c
statistical
v cc x-513
v;
model
v-1
7 " x-1
t Coxis
moves at a time but in such a way that the (nn) condition is not
broken. As this process involves motion where the neighbors
are coupled by EQQ interaction, we can anticipate that it is
much slower than the hopping of single excitations. The
position of the IP and OP pairs in the lattice and their energy
states are shown in Fig. 2. For the IP pairs, the lowest two states
are separated by A/kB 6 5 mK; whereas for the OP pairs,
A(OP)/kB = 64 mK. Hence the energy involved, if an IP pair is
transformed into an OP pair by a jump of one particle, is in the
order of A(0P) and much larger than the width 6 of the rational
states. This process is, therefore, unlikely.
Van Kranendonk's result for IP pairs, [27] of ref. 25, can be
rewritten as (1)
with vo given by [2]. Unfortunately, 6 is quite uncertain, and a
value 6 / h = 30 MHz, as measured in microwave pair spectra
(12), is adopted. This leads to
which has to be compared with [2] for single excitations.
Furthermore, it has been noted that a single impurity can jump to
12 nn sites, but a pair can only make four different jumps.
Hence, the ratio of the times spent on a given site is tlP/ts =
3(vs/vlp). As for the OP pairs, a calculation for kBT >> A(OP)
shows that vOp/vlp = 0.3. Each hopping of an OP pair involves
the probability p = exp (-AE/kBT) of an excited state with
energy A(0P). As T is decreased, p decreases and so does vop.
It is calculated that for kBT < A(OP), vop/vIp is SO small that
comparatively speaking, the OP pair can be considered immobile. Then, if we assume that each encounter of two pairs leads
to a cluster formation and hence to disappearance of the pairs,
Van Kranendonk's rate equations show that the disappearance
time, T(O,), is three times slower than T ( ~ PThis
) . result can be
directly compared with experimental data (5). The theory has
not yet yielded a prediction on the temperature dependence of
the observed pair-decay rate. Based on geometrical arguments,
Van Kranendonk (25) has concluded that clusters of three (nn)
0-HZor more cannot displace themselves.
3.. Experiments
3.1. Redistribution of single excitations
In general, the experimental procedure has consisted of
monitoring an appropriate physical quantity (such as optical
signal intensity, specific heat, thermal conductivity, etc.) versus
time at an initial temperature. After the H2 sample was rapidly
cooled (or warmed) to a new temperature and a thermal
equilibrium was reached, measurements were carried out versus
time at this temperature until they indicated an equilibrium state
has been reached. From the change with time, usually represented by an exponential decay, an experimental time constant T
1457
MEYER
was obtained, which corresponded to the motion tacitly assumed to be that of the "singles." (As was discussed above, the
hopping motion of pairs is slower than that of singles.)
The data obtained so far show clear trends, but there has been
a surprising amount of inconsistencies and scatter among the
various results and much remains to be done to clarify the
experimental situation. The reason for the scatter among the
different sets of experiments is not understood. However, it is
possible that the crystallization procedure, which is no doubt
nearly the same for each sample in a given series of experiments but probably different among the various research
groups, plays a role in influencing the clustering reaction time.
This is consistent with Van Kranendonk's predictions (1) that
the hopping frequency depends on the interaction between
lattice vibrations and the angular momenta, and hence on the
strains and defects in the crystals.
Probably the most direct- information on the clustering has
been provided by nrnr and spectroscopic methods, where a
signal intensity proportional to the number of singles and (or)
pairs is monitored as a function of time. As the IP and OP pairs
have different energy-level spectra because of differences in
crystalline-field interactions, the microwave experiment by
Hardy et al. (12) that measured transitions between these levels
was able to give different signals for the two species. This
experiment required a low concentration, X < 2 x l o p 3 , to
produce sufficiently sharp lines. After the temperature was
rapidly decreased and stabilized at a certain value, the intensity
of these pairs was found to increase but with different relaxation
~
7 ~1 p , ~,where
,
~ the subscript O P or IP defines the
times, T
pair in question and G means "growth" from singles. This
transient is shown in Fig. 3.
From nmr experiments, the spectrum of "singles", OP, and IP
pairs could be observed in single crystals at appropriate angles
with respect to the magnetic-field direction (5). After rapidly
decreasing T and stabilizing it, the intensity of the singles was
found to decrease with time while that of both O P and IP pairs
were found to increase, all with the same time constant, as
shown in Fig. 4. Here T,(S+ OP, IP) = 7 0 p . ~= 7 1 p , ~and this
result is therefore inconsistent with that by Hardy er al. (12).
However unpublished measurements' of the intensity of microwave absorption lines for X > 0.002 as a function of time seem
to indicate that the difference between the IP and the O P growth
rates is not well established, and more experiments are needed.
In Fig. 5 , the transient in three other measurements (pressure,
ortho-to-para conversion heat, thermal conductivity) is shown
versus time, where it can be seen that a simple exponential law is
followed from which a time 7 can be determined. One can
estimate that. on average. 7 can be determined to about 10% or
even better, and therefore the differences among the data are a
real effect and are not caused by poor precision or ambiguity in
the measurement of 7 .
To discuss the various results, we find it useful to show in Fig.
6 a general trend of the concentration dependence of 7 at two
reference temperatures, 1.2 and 2.1 K , with data from several
research groups. Generally, 7 increases with decreasing X but
tends to saturate below X = 0.01 and for T S 1.5K. Very
roughly, most of the experimental evidence indicates a trend
expressed by
( a ) - GROWTH
OF PAIR INTENSITIES
X=O.Zo%;
T = 1.2K
3.0
0
GI
OUT OF PLANE
13.65 GHz
A,
64.15 GHz
:2.0
a
--
20
10
TlME
k
V)
z
1.0,
(b)-
IN PLANE
84.1 GHr
30
40
(h)
DECAY
+
Z
a
0
W
0.5-
----
------------------
0 - -
TlME ( h )
TIME
(h)
1458
TIME (h)
,T-'" mm ==10.7,
,
refs. 4 , 5 , 6 , 11
ref.7
that reflects the "high" and the "low" temperature behavior can
express the data quite well and is shown by a solid line in Fig. 8.
For T 5 0.05K, the rate was found to be too fast for
measurement with the procedure outlined above, where the H2
sample was cooled together with the dilution refrigerator from
1.5 K, a process requiring approximately 1.5 h. This fast
clustering rate was found on a number of other crystals
investigated via the nmr spectrum. A few hours after cooling
below -0.07 K , the nmr signal of the singles near the center of
the H2 spectrum could not-be detected any more. Ain obvious
next step will be keeping the dilution refrigerator operating at
T 5 0.07 K and rapidly establishing or breaking the thermal
contact with the sample by means of a heat switch. In that
modification, the sample can be warmed up to -2 K to uncluster
for a period of several hours before the next rapid cooling for a
further clustering experiment.
However, Fig. 8 shows a discrepancy with the recent
Kharkov data (7). In these latter experiments, T is obtained from
the time-dependent specific heat for T > 1 K and from the
energy release due to ortho-para conversion for T < 1 K for
0.1% IX I1.1%. These data show a T-I dependence of T.
Also nmr data by Kohl (27) show an increase of T to 19 h at
0.12 K and no evidence of a maximum.
From the variation of the thermal conductivity with time
during clustering (13), it has been concluded that this method is
a very suitable one for a systematic study of T over a wide range
of X and T, and such measurements are planned for the near
future.
Minchina et al. (26) have- extended their calorimetric
experiments to solid H2-D2 mixtui-es and measured the reaction
time T for several mole fractions X(D2) of D2, where the initial
impurity concentration X of 0-H2 was between 0.5% and 1%.
As in pure HZ,they found T to rise with decreasing temperature.
A surprising result, shown in Fig. 9, is that the lowest value of T
along an isotherm was measured not for pure H2 but for a
concentration of 2% D2. Second, even high concentrations of
30% D2 led to an increase of T by a factor of less than 2. These
findings contradict earlier calorimetric experiments by Roberts
and Daunt (28), who reported that for a mixture of 15% D2 in
Hz, quantum diffusion is suppressed. Finally, Minchina et al.
1459
MEYER
#2, X=0.002
T =0.025K 1
--
O P Poir decoy
+.v I P Poir decoy
0
I
0.1
60
40
TlME
20
80
(h)
0.2 0.3
FIG.9. The reaction time in H2-D2 mixtures versus D7 concentration, X(D2), at two temperatures. From Minchina et 01. (26).
"'
Singles
Y
o0 ~
"
OP Pairs
"
I0
"
~15 "
'
20
"
"
25
TlME ( h )
1460
1461
MEY ER
X
FIG. 13. The line width of H(HD) with -300ppm HD in H, crystal
IV versus the concentration X(o-Hz). The open circles are the results
for long rfpulses, while the closed circles are those for short rfpulses.
From Washburn el nl. (38) and Yu (39).
one calculated (33) for the rigid lattice (Fig. 13, curve labeled
ST) and the one calculated (33) from nmr data (3) of 0-HZ
impurities in p-Hz (line labeled B). Hence, it was believed that
motional narrowing was detected with a hopping frequency in
the order of 2kHz, which is consistent with the estimations.
However, Yu (39) has pointed out that the true line width must
be obtained from short-pulse sequences (< 10 p s , solid circles
in Fig. 13) to reflect the true dipolar interactions with the
surrounding HZ.For short pulses, experiments at Duke University have indicated only little exchange narrowing, as shown in
Fig. 13. Hence, Yu concludes that the hopping frequency is
insignificant. More experiments are necessary to resolve this
discrepancy with theory.
3.46. Recombination of H atoms in hexagonal close-packed
HZ
For a number of years, there has been an interest in studying
the interactions between atomic H embedded in a solid H,
matrix and the surrounding molecules. The first studies of the
recombination rate of H in this matrix as a function of
temperature were made by Leach (40). He produced H atoms in
HZby using pulsed electron injection from an accelerator into a
microwave cavity of an electron paramagnetic resonance (EPR)
spectrometer. The intensity of the EPR signal was then
measured as a function of time. It was found that in the
temperature range between 6 and 8 K, the recombination rate
was proportional to exp -(E,/kBT) with an activation energy
E,/kB = 200 K, which is the same as that for the diffusion of H2
in solid Hz (3). However, he found that at 4.2 K, the rate was
lo4 times faster than the extrapolation from higher temperature
indicated. He ascribed this to phonon-assisted tunneling characterized by a much lower activation energy. However, he did not
report on recombination measurements below 4.2 K.
A more complete study of the recombination rate was
reported by Katunin et al. (41). They condensed a beam,
consisting of a mixture of hydrogen atoms and molecules
produced in a radio-frequency dissociator, into a microwave
cavity of an EPR spectrometer. They found that above 4.5 K ,
the recombination rate was again proportional to exp -(E,/kBT)
but with E,/kB = 1 10 K, roughly half the value found by Leach
(39). At temperatures below 4.5 K, the recombination rate was
much larger than expected from such an activation energy, and
the authors concluded that diffusion of the H atoms had to
1462
Acknowledgments
Support of this research by the National Science Foundation
through Grant D M R 8516156 is gratefully acknowledged. The
author has greatly appreciated detailed comments and suggestions on this manuscript by R. G . Palmer and J. van Kranendonk. Stimulating conversations with W. N . Hardy, N . S.
Sullivan, and H. G. Robinson are also acknowledged as well as
R. P. Behringer's comments o n an early draft. H . Ishimoto
attracted the author's attention to ref. 41.
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