pubs.acs.org/JPCC
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
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structure
stoichiometry (H2:H2O)
sII
C1
48:136
6:36
C2
8:8
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 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.
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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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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REFERENCES
(1) Sloan, E. D.; Koh, C. A. Clathrate Hydrates of Natural Gases, 3rd
ed.; CRC, Taylor Francis: Boca Raton, FL, 2008.
(2) Loveday, J. S.; Nelmes, R. J.; Klug, D. D.; Tse, J. S.; Desgreniers,
S. Can. J. Phys. 2003, 81, 539.
(3) Hirai, H.; Tanaka, T.; Kawamura, T.; Yamamoto, Y.; Yagi, T.
J. Phys. Chem. Solids 2004, 65, 1555.
(4) Loveday, J. S.; Nelmes, R. J. Phys. Chem. Chem. Phys. 2008,
10, 937.
(5) Vos, W. L.; Finger, L. W.; Hemley, R. J.; Mao, H. K. Phys. Rev.
Lett. 1993, 71, 3150.
(6) Londono, D.; Kuhs, W. F.; Finney, J. L. Nature 1988, 332, 141.
(7) Machida, S.; Hirai, H.; Kawamura, T.; Yamamoto, Y.; Yagi, T.
J. Chem. Phys. 2008, 129, 224505.
(8) Dyadin, Y. A.; Larionov, E. G.; Manakov, A. Y.; Zhurko, F. V.;
Aladko, E. Y. Mendeleev Commun. 1999, 5, 209.
(9) Dyadin, Y. A.; Larionov, E. G.; Aladko, E. Y.; Manakov, A. Y.;
Zhurko, F. V.; Mikina, T. V.; Komarov, V. Y.; Grachey, E. V. J. Struct.
Chem. 1999, 40, 790.
(10) Mao, W. L.; Mao, H. K.; Goncharov, A. F.; Struzhkin, V. V.;
Gou, Q. Z.; Hu, J. Z.; Shu, J. F.; Hemley, R. J.; Somayazulu, M.; Zhao,
Y. S. Science 2002, 297, 2247.
(11) Lokshin, K. A.; Zhao, Y. S.; He, D. W.; Mao, W. L.; Mao, H. K.;
Hemley, R. J.; Lobanov, M. V.; Greenblatt, M. Phys. Rev. Lett. 2004,
93, 125503.
(12) Mao, W. L.; Mao, H. K. Proc. Natl. Acad. Sci. U.S.A. 2004,
101, 708.
(13) Lokshin, K. A.; Zhao, Y. S. Appl. Phys. Lett. 2006, 88, 131909.
(14) Emchenko, V. S.; Antonova, V. E.; Barkalov, O. I.; Klyamkin,
S. N.; Tkacz, M. High Pressure Res. 2009, 29, 250.
(15) Antonova, V. E.; Emchenko, V. S.; Tkacz, M. J. Phys. Chem. B
2009, 113, 779.
(16) Hammersley, A. P. ESRF Internal Report ESRF97/HA02T;
European Synchrotron Radiation Facility: Grenoble, France, 1997.
(17) Hirai, H.; Ohno, S.; Kawamura, T.; Yamamoto, Y.; Yagi, T.
J. Phys. Chem. C 2007, 111, 312.
(18) Vos, W. L.; Finger, L. W.; Hemley, R. J.; Mao, H. K. Chem. Phys.
Lett. 1996, 257, 524.
(19) Kurnosov, A. V.; Manakov, Y. Y.; Komarov, V. Y.; Voronin,
V. I.; Teplykh, A. E.; Dyadin, Y. A. Dokl. Phys. Chem. (Transl. of Dokl.
Akad. Nauk) 2001, 381, 303.
(20) Hirai, H.; Uchihara, Y.; Nishimura, Y.; Kawamura, T.; Yamamoto, Y.; Yagi, T. J. Phys. Chem. B 2002, 106, 11089.
(21) Londono, D.; Finney, J. L.; Kuhs, W. F. J. Chem. Phys. 1992,
97, 547.
(22) Emchenko, V. S.; Kuzovnikov, M. A.; Fedotov, M. K.; Simonov, S. V.; Tkacz, M. J. Alloys Compd. 2011 in press.
(23) Lager, G. A.; Jorgensen, J. D.; Rotella, F. J. J. Appl. Phys. 1982,
53, 6751.
(24) Moulton, N. E.; Watson, G. H.; Daniels, W. B.; Brown, D. M.
Phys. Rev. A 1988, 37, 2475.
4902
ARTICLE
(25) Sharma, S. K.; Mao, H. K.; Bell, P. M. Phys. Rev. Lett. 1980,
44, 886.
(26) Eggert, J. H.; Hemley, R. J.; Mao, H. K.; Feldman, J. L. AIP Conf.
Proc. 1994, 309, 845.
(27) James, H. M.; Van Kranendonk, J. Phys. Rev. 1967, 164, 1159.
(28) Diatshenko, V.; Chu, C. W.; Liebenberg, D. H.; Young, D. A.;
Ross, M.; Mills, R. L. Phys. Rev. B 1985, 32, 381.
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