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pubs.acs.org/JPCC

Phase Behavior of H2 H2O at High Pressures and Low Temperatures

Timothy A. Strobel,* Maddury Somayazulu, and Russell J. Hemley
Geophysical Laboratory, Carnegie Institution of Washington, 5251 Broad Branch Road NW, Washington, D.C. 20015, United States
ABSTRACT: Whereas several clathrate-like structures are known to exist
from mixtures of H2 H2O under pressure, the combined high-pressure
and low-temperature region of the phase diagram remains largely unexplored. Here we report a combined Raman spectroscopy and synchrotron X-ray diraction study on the low-temperature region of the phase
diagram. Below 120 K, the H2 vibron originating from the clathrate 2
(C2) phase splits into two distinct components, yet X-ray diraction
measurements reveal no structural change between room temperature and
11 K. We suggest that the two vibrons of the C2 phase at low temperature originate from vibrational transitions of hydrogen
molecules in the ground and rst excited rotational energy levels. At 1 GPa we observe the clathrate 1 (C1) phase to persist to the
lowest temperature measured (80 K). Upon decompression from the C2 phase we observed the appearance of cubic ice (Ic), which
converted to a new phase before transforming to the C1 phase. The structure of the new phase is consistent with a water framework
similar to R-quartz; the structure could also be related to the tetragonal clathrate phase reported previously for nitrogen and argon
guests.

I. INTRODUCTION
Under conditions of high pressure and/or low temperature,
mixtures of water and small molecules may crystallize into structures
called clathrate hydrates.1 True clathrate hydrates consist of hydrogen-bonded water molecules arranged in polyhedral cavities which
trap small guest molecules such as argon or methane. Similarly, small
molecules may stu the void spaces of ice phases, forming lled
ices. In general, open-network clathrate hydrate structures go
through a series of structural transformations with pressure, eventually transforming into dense lled ices.2-4 Filled-ice phases, while
not true clathrate hydrates, are often referred to as clathrates due to
the similar guest-host relationship; herein, this nomenclature is
maintained.
In 1993, Vos et al.5 reported the formation of two lled-ice
clathrates. At room temperature, H2 H2O mixtures crystallize into
the C1 (clathrate 1) phase at 0.7 GPa. The C1 structure is based
upon the framework of ice II (R3). When viewed with hexagonal
axes, the unit cell of the C1 phase contains 36 water molecules, in a
channel-like arrangement, which host six hydrogen molecules. The
lattice constants at 2.1 GPa are a 12.7 and c 6.0 . The C1
phase is unique for water-based clathrates in the sense that the
protons are ordered. This H2 H2O C1 phase is isostructural with
the helium-lled-ice phase reported by Londono et al.6 Further
compression of the H2 C1 structure at room temperature results in
the formation of a second lled-ice clathrate (C2) at 2.3 GPa. The C2
phase is based on the diamond structure of cubic ice (Ic) (Fd3m) and
may be viewed as two interpenetrating fcc lattices (as in ice VII) with
points of one lattice occupied by proton-disordered H2O and the
other by rotationally disordered H2. The unit cell of C2 contains eight
water molecules and eight hydrogen molecules with a 6.4 at
3.1 GPa. At ambient temperature, the C2 structure is stable to at
least 40 GPa, above which a denser structure was suggested to persist
to at least 80 GPa.7
r 2011 American Chemical Society

Aside from the C1 and C2 phases, structure two (sII) clathrate

hydrate is the only additional clathrate phase currently known for
H2 H2O mixtures. The unit cell of sII consists of 136 water
molecules arranged into eight hexakiadecahedral (51264) and
sixteen pentagonal dodecahedral (512) hydrogen-bonded polyhedral cavities. The formation of the sII phase was originally
inferred from phase equilibrium data8,9 and later conrmed
through spectroscopic and diraction measurements.10 Completely lled sII clathrate contains 48 H2 molecules in the a 17.1
Fd3m unit cell.11 The stability of this phase extends from 150 K
at ambient pressure to 274 K at 0.36 GPa. Above 0.36 GPa
available experimental evidence suggests this phase transforms
into C1.8-10,12-15 Structural parameters for the various H2
H2O clathrate phases are provided in Table 1.
While the ambient temperature phase behavior of H2 H2O
mixtures has been widely studied, low-temperature measurements under pressure are extremely limited. We are aware of only
one preliminary Raman result for the C2 phase at 77 K.12 Studies
at low temperature may reveal additional phases and structural
complexity observed in clathrate-forming systems with similar
guests. These results are pertinent to hydrogen-rich interstellar
ices and may reveal novel high-density hydrogen storage materials. In this work we performed a combined Raman and synchrotron X-ray diraction study of the H2 H2O system from 0.3 to
5 GPa between 11 and 300 K.

II. EXPERIMENTAL METHODS

Mixtures of H2 H2O were prepared in copper-beryllium
(CuBe) piston-cylinder diamond anvil cells containing 300 m
Received: December 24, 2010
Revised:
January 30, 2011
Published: February 28, 2011
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diameter anvil culets and CuBe gaskets. A drop of ultrapure H2O

(HPLC grade, Alfa Aesar) was placed into the 150 m
diameter gasket hole with a ruby sphere for pressure calibration.
The cell was assembled, and the piston was oscillated several
times within the cylinder until an air bubble (100 m) was
trapped. The cell was then placed inside a high-pressure gasloading apparatus, and the air bubble was displaced by H2 at 0.2
GPa. All measurements were performed on samples with excess
hydrogen to avoid the formation of any pure H2O ice phases.
Once the H2 bubble was contained in the cell, the compressive
force was transferred to a lever-arm assembly to enable pressure
change within a cryostat.
Raman spectra were obtained on the C2 phase between 3.4
and 5.1 GPa from 300 to 77 K. Temperature was controlled by
the regulation of liquid nitrogen in an open-ow cryostat
(Cryoindustries) with a cooling rate of approximately 1.5 K/
min. Spectra were obtained using a Princeton Instruments
spectrograph (SP2300, Trenton, NJ) using the 488 nm line of
an Ar laser as an excitation source with 20 mW power. Laser
light was focused on the sample using a 10 long working
distance objective lens, and Raman light was collected in the
backscatter geometry through a 50 m spatial lter. Scattered
light was passed though a 50 m slit and dispersed o of a 1500
gr/mm grating onto a liquid nitrogen cooled charge-coupled
device (CCD) detector.
Powder X-ray diraction measurements were performed at
the High Pressure Collaborative Access Team (HPCAT), beamline 16-IDB, of the Advanced Photon Source, Argonne National
Table 1. Structural Parameters for H2 H2O Clathrate
Phases
ideal unit cell
phase

structure

stoichiometry (H2:H2O)

sII
C1

cubic (Fd3m), a 17.1

trigonal (R3), a 12.7 , c 6.0

48:136
6:36

C2

cubic (Fd3m), a 6.4

8:8

Laboratory. Temperature was controlled by the regulation of

helium in an open-ow cryostat, and pressure was determined by
uorescence from a ruby standard using an online measurement
system. A monochromatic beam (5  5 m2) with = 0.36821
was focused on the sample, and data were recorded using a
MAR image plate. Diraction images were processed using the
FIT2D16 data analysis program.

III. EXPERIMENTAL RESULTS

When the sample was compressed to 3.0 GPa at 300 K, Raman
spectra obtained from the hydrogen roton, OH stretching, and
hydrogen vibron regions were consistent with previous reports of
the C2 phase.3,5,17,18 The sample was spatially homogeneous, and
we observed no spectral characteristics originating from ice VII.
The existence of excess hydrogen was veried by the presence of
bulk H2 roton and vibron modes, but we were able to spatially
resolve the pure clathrate phase. Upon initiation of cooling, the
sample pressure increased due to the thermal contraction of the
cell. Down to 120 K, we observed no signicant changes in the
Raman spectra of the C2 phase other than the sharpening of the
Raman peaks associated with thermal uctuations. At 120 K, a
small shoulder developed at 11 cm-1 higher frequency than the
hydrogen Q1(1) vibron. The intensity of this contribution
increased with decreasing temperature and was clearly resolved
at 77 K (Figure 1).
While we observed no indication of a structural change in
other regions of the Raman spectra (e.g., OH stretch, Figure 1),
the appearance of the high-frequency vibron may be indicative of
a structural transformation (i.e., hydrogen within a new chemical
environment). To probe this possibility, we performed synchrotron X-ray diraction measurements on the C2 phase at 4.1 ( 0.3
GPa from 300 to 11 K. Figure 2 shows X-ray diraction patterns
obtained from the C2 phase as a function of temperature. At 288
K and 4.1 GPa the diraction pattern was indexed to the C2 Fd3m
structure with a = 6.393(1) , in good agreement with previous
reports.5,17 Upon cooling to 11 K, we observed no indication of a
structural phase transition and observed the persistence of the C2

Figure 1. Raman spectra of the H2 vibron (left) and OH (right) regions of the C2 phase with decreasing temperature. A high-frequency shoulder
appears in the vibron spectra marked by the arrows. Between 178 and 77 K the pressure increased from 4.2 to 5.1 GPa.
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Figure 2. X-ray diraction patterns of C2 from 288 to 11 K at 4.1 (

0.3 GPa. Miller indices are indicated, and gasket contributions are
labeled g.

phase over the entire temperature range. We obtained additional

data points at 5 GPa (56 and 82 K) and at 3 GPa (100 K), only
observing the C2 phase.
The sample was decompressed from 3.0 GPa and 100 K to
obtain additional information about the low-temperature phase
diagram. While we attempted to decompress in a controlled
manner, the pressure dropped rapidly to 0.3 GPa at 110 K. Under
these conditions, the diraction peaks broadened and shifted to
higher angles. The decrease in d spacing with decreased pressure
indicates a phase transformation as decreased pressure is generally concomitant with lattice expansion. At 0.5 GPa and 145 K,
the diraction pattern was indexed to the space group Fd3m with
a = 6.24(2) consistent with the formation of Ic, which is
contracted relative to the C2 lattice (Figure 3).
The pressure increased to 0.6 GPa as the sample continued to
warm to 168 K, and several new diraction peaks were observed.
At 0.73 GPa and 172 K the Ic phase disappeared completely. We
were unable to index the patterns obtained at these conditions to
any common ice or clathrate phases. The observed reections
were successfully indexed to a trigonal lattice with a = 6.24 and
c = 6.18 . These reections can also be described by a tetragonal
lattice with a = 6.25 and c = 10.67 , similar to reports of the
high-pressure P42/mnm tetragonal clathrate structure observed
previously for argon19,20 and nitrogen2 guests (a 6.3 , c
10.6 ). We were unable to collect additional data on this phase
as the temperature and pressure were stabilizing during this
period in the experiment and small pressure-temperature (PT) changes prompted another phase transition.
As the pressure and temperature stabilized to 0.73 GPa at 170
K, many new peaks appeared in the diraction patterns. These
new peaks were successfully indexed to the C1 structure with a =
12.986(6) and c = 6.205(4) . As time progressed the intensity
of the diraction peaks from the new phase decreased relative to
that of the C1 contributions. From 0.73 GPa and 170 K, we
cooled the sample again to explore the phase diagram further.

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Figure 3. Diraction patterns obtained before and after C2 decompression. Indexing of the new phase is shown for the trigonal and tetragonal
lattices, and simulated patterns are shown assuming the C022 and Rquartz23 structures (see the text). Tick marks for the various phases are
displayed in the respective patterns, and contributions form the gasket
material are indicated by g.

Upon cooling to 80 K, the sample consisted almost entirely of C1

with a small amount of the new phase (Figure 4). The pressure
increased to 1.2 GPa upon cooling. At 80 K the C1 diraction
pattern was described well by a simulated pattern with a =
12.851(3) and c = 6.140(2) using oxygen atom positions
from Londono et al.21

IV. DISCUSSION
Diraction data obtained in this study help to extend the phase
stability limits into the low-temperature regime for both the C1
and C2 structures. At 4.1 ( 0.3 GPa C2 is stable at room
temperature and persists to the lowest temperature studied (11
K). At 1.05 ( 0.15 GPa the C1 phase persists to the lowest
temperature reached (80 K). These observations constrain the
P-T phase diagram of H2 H2O. On the basis of our
observations, we propose an extended phase diagram shown in
Figure 5.
During decompression to 0.3 GPa we observed the disappearance of the C2 phase and the formation of ice Ic. This process
occurred over a period of minutes and is likely a metastable
phenomenon. We expect that the true equilibrium structure at
0.3 GPa and 110 K is sII on the basis of previous observation of
this phase at similar conditions.12 We speculate that the C2 phase
transformed directly to ice Ic upon rapid decompression without
going through the intermediate C1 phase (or other phases). Ice Ic
may be viewed as the same structure as C2 without hydrogen and
likely represents a low-barrier pathway to a local energy minimum. Indeed, isothermal decompression of C2 from 2.3 GPa at
77 K resulted in decomposition at 0.35 ( 0.05 GPa in a previous
Raman study.12
Subsequent to the structural collapse of C2 to ice Ic and prior
to the recrystallization of C1, we observed diraction from an
unidentied phase in a small P-T interval near 0.7 GPa and 170
K. We are unable to condently assign this phase at present, but
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Figure 4. Diraction patterns obtained from the (predominantly) C1

phase upon cooling at 1.05 ( 0.15 GPa. The lower pattern is a simulated
prole for the C1 structure, and tick marks indicate allowed reections
for the C1 phase. Asterisks show reections remaining from the new
phase, and g shows gasket contributions.

indexing is consistent with a trigonal or tetragonal lattice. In the

case of the trigonal lattice, we are unaware of any known clathrate
or ice-based structures that can reproduce the observed diraction pattern. In the tetragonal case, this structure might be similar
to previously reported clathrate structures for argon and nitrogen; however, several diraction lines were not observed, and
calculated diraction intensities were not well matched.
Pressure-induced phase transformations in clathrates typify
structural densication through application of pressure. At low
pressure, small clathrate-forming guest molecules take on the
most open structures (sI, sII), gradually transforming to dense
lled ices upon pressure increase.2-4 In general, the order by
which structural transitions proceed is directly related to the size
of the guest molecule: the smaller the molecule, the lower the
lled-ice transition pressure. The diameter of the hydrogen
molecule dictated the common consensus that its lowest pressure
structure was lled ice until it was realized that multiple
occupants of a single cavity could stabilize sII.10 The native
low-pressure structure for both Ar and N2 clathrates is sII. The
slightly smaller Ar atom gives rise to transitions from sH, sT, and
hexagonal lled ice at approximately 0.5, 0.7, and 1.1 GPa,
whereas the larger N2 molecule goes though the same transitions
at 0.8, 1.3, and 1.6 GPa, respectively.3 On the basis of comparisons
with other clathrate-forming systems, and our observations of new
diraction lines, it is reasonable to suggest a region of stability for a
new clathrate structure of hydrogen. This region would logically exist
between the least dense native sII and the rst lled-ice phase
exactly where we observed new diraction features.
Emchenko et al.22 recently reported the formation of a new
H2 H2O phase identied from quench-recovered samples
formed at 253 K and 0.5 GPa. On the basis of similarities in
formation conditions and experimental X-ray diraction patterns, this phase appears to be identical to the one we report here.
Additionally, the independent observation using dierent experimental techniques and P-T paths for synthesis suggests that this phase has a eld of thermodynamic stability.

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Figure 5. Proposed phase diagram for H2 H2O (>50 mol % H2).

Small open circles represent experimentally determined phase boundaries compiled from various sources;5,8,9,12-15,28 solid lines through
these data guide the eye. Larger lled symbols show P-T conditions
where diraction data were obtained in this study: red triangles, C2; blue
squares, ice Ic; yellow tilted squares, new phase; green circles, C1. The
dotted orange arrows trace the P-T path followed in this study.
Dashed-dotted lines extrapolate phase boundaries on the basis of
available data. The hatched region of the phase diagram indicates
uncertainty and the possible location of a new phase. L = liquid, F =
uid, and S = solid.

Emchenko et al.22 suggested the structure of the new C0 phase

has trigonal symmetry (P3112) with a = 6.33 and c = 6.20
(ambient pressure), and three unique oxygen atom positions to
describe the preliminary structure: O1 at the 3a positions with x
= 0.23 and full site occupancy, O2 at the 3b positions with x =
0.75 and full site occupancy, and O3 at the 3a positions with x =
0.1 and half site occupancy.
While the structure proposed by Emchenko et al.22 is capable
of reproducing diraction features observed in both experimental
studies, variation in observed diraction intensities (i.e., texture)
precludes a denitive description. Additionally, the proposed
structure is unusual with respect to the half-occupied oxygen
positions. We nd that the general characteristics of the diraction patterns are reproduced well by assuming a structure based
on the framework of R-quartz23 (Figure 3). Reections allowed
for the R-quartz structure (P3221) are identical to those of the
proposed P3112 structure. While we are unaware of any ice-based
analogues to the R-quartz structure, it readily satises the
tetrahedral bonding requirements of water. Unfortunately, our
patterns were not suitable for Rietveld analysis; nevertheless, this
model serves as a basis for future structural studies.
Our initial structural study was prompted by the appearance of
a new H2 vibron at higher frequency than the Q1(1) vibron of the
C2 phase (Figure 1). However, our low-temperature diraction
data clearly rule out the possibility of a low-temperature phase
transition at 4 GPa. To reconcile these observations, we must
consider the nature of the H2 Q branch at high pressure and low
temperature. For the isolated H2 molecule at room temperature
(and at low density), the Q branch of the Raman spectrum
of hydrogen consists of four sharp lines (with appreciable
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intensity). These excitations represent transitions from the
ground to rst excited vibrational energy levels () for molecules
in each of the four most populated rotational energy levels (J) at
room temperature. Namely, Q(J), where = ( = 0 f = 1) = 1
and J = 0, 1, 2, and 3. At room temperature, these sharp lines
broaden nonlinearly with increasing pressure until only a single
peak (Q1(1)) is observed at 1.0 GPa; above this pressure
rotational ne structure is not observed.24,25
This situation, however, is not the case at low temperature. In
the low-temperature uid and solid H2 phases, both the Q1(1) and
Q1(0) contributions are observable with Raman spectroscopy.26
Assuming a rigid quantum rotor model and Boltzmann energy
distribution, the populations of the rst and second rotational
energy levels account for >99% of all occupied states at 77 K, and
higher energy rotations may be neglected. For the isolated molecule,
separation between the Q1(0) and Q1(1) lines is 6 cm-1. Studies
on pure H2 at 77 K revealed the divergence of the Q1(1) and Q1(0)
lines with pressure, reaching 20 cm-1 separation at 3 GPa.26
Additionally, the intensity ratio of Q1(0) to Q1(1) drops rapidly
from 0.25 at ambient pressure to 0.025 at 2.5 GPa.26 This behavior
is rationalized by considering that a J = 0 impurity within a J = 1
lattice induces its neighbors to oscillate out of phase, due to its higher
vibrational energy, thereby reducing the overall polarizability.27 The
appearance of a higher energy vibron band in the low-temperature
C2 phase is consistent with the behavior of bulk hydrogen in this PT range.26 Therefore, like bulk H2, the second vibron can be
attributed to a vibrational transition of hydrogen in the lowest lying
rotational energy level, i.e., Q1(0). The weak intensity of this band
and energy separation from Q1(1) (11 cm-1) are both consistent
with observations in bulk hydrogen.26 We note that unassigned
high-energy vibron peaks were also observed at 77 K in a related
low-temperature C2 Raman study.12

V. CONCLUSIONS
A combined Raman spectroscopy and synchrotron X-ray diraction study was performed to explore the high-pressure and lowtemperature region of the H2 H2O phase diagram. Below 120 K,
the H2 vibron originating from the C2 phase splits into two distinct
components. The appearance of a second higher energy vibron is
consistent with vibrational transitions of hydrogen molecules in the
ground and rst excited rotational energy levels, and diraction
measurements indicate that the C2 phase persists to 11 K. At 1 GPa
we observe the C1 phase to persist to 80 K. This information helps to
extend the stability limits of the C1 and C2 phases on the H2 H2O
P-T phase diagram. Upon decompression from the C2 phase we
observed the appearance of Ic, which transformed to a new phase
before transforming to C1. This new phase is consistent with a water
framework based on the structure of R-quartz, but could also be
related to the tetragonal clathrate structure reported previously for
nitrogen and argon guests. These results are directly applicable to PT conditions of hydrogen-rich interstellar ices and may help to reveal
novel high-density hydrogen storage materials.
AUTHOR INFORMATION
Corresponding Author

*E-mail: tstrobel@ciw.edu.

ACKNOWLEDGMENT
We thank S. Sinogeikin for assistance with the X-ray diraction
measurements. This work was designed and executed under the

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U.S. Department of Energy, Oce of Basic Energy Sciences

(DOE-BES) (Grant DE-FG02-06ER46280). Funding from the
National Science Foundation, Division of Materials Research
(NSF-DMR) (Grant DMR-0805056), and DOE National
Nuclear Security Administration (NNSA) (Grant DE-FC5208NA28554) is acknowledged for instrumentation support during the experiments. Portions of this work were performed at
HPCAT (Sector 16), Advanced Photon Source (APS), Argonne
National Laboratory. HPCAT is supported by the Carnegie
Institution of Washington (CIW), University of Nevada, Las
Vegas (UNLV), and Lawrence Livermore National Laboratory
(LLNL) through funding from DOE-NNSA, DOE-BES, and
NSF. APS is supported by DOE-BES under Contract DE-AC0206CH11357.

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