1 Pressure-induced decomposition of solid hydrogen sulfide Defang Duan, Xiaoli Huang, Fubo Tian, Da Li, Hongyu, Yu, Yunxian Liu, Yanbin Ma, Bingbing Liu, Tian Cui a) State Key Laboratory of Superhard Materials, College of Physics, Jilin University, Changchun 130012, People’s Republic of China a) Electronic address: [email protected]Solid hydrogen sulfide is well known as a typical molecular crystal but its stability under pressure is still under debate. Particularly, Eremets et al. found the high pressure superconductivity with T c 190 K in a H 2 S sample [arXiv: 1412.0460 (2014)] which is associates with the elemental decomposition into H 3 S [Sci. Rep. 4, 6968 (2014)]. Therefore, on what pressure H 2 S can decompose and which kind of the products of decomposition urgent need to be solved. In this paper, we have performed an extensive structural study on different stoichiometries H n S with n> 1 under high pressure using ab initio calculations. Our results show that H 2 S is stable below 50 GPa and decomposes into H 3 S and sulfur at high pressure, while H 3 S is stable at least up to 300 GPa. The other hydrogen-rich H 4 S, H 5 S, and H 6 S are unstable in the pressure range from 20 to 300 GPa.
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Pressure-induced decomposition of solid hydrogen sulfide
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Pressure-induced decomposition of solid hydrogen sulfide
f.u./cell) at 200 GPa. For the structure of H4S, H5S, and H6S at 200 GPa, there is a
common feature that they all consist of H3S Im-3m blocks interbedded H2 molecular
units forming sandwich type structure. This suggests the possibility of decomposition
to mixture H3S and H2. In contrast, H2 molecular units disappear in H6S-Pbcn
structure characteristic as six H-S bonds in the H6S molecular unit at 300 GPa, as
shown in Fig. 4d. It suggests that H6S may become stable at higher pressures.
V. Conclusions
In summary, we explore the phase stabilities and the structures of different
stoichiometries HnS (n>1) between 20 and 300 GPa through ab initio calculations.
The results demonstrate that H2S decompose to H3S and sulfur above 50 GPa and H3S
is stable up to 300 GPa. By contrast, the other hydrogen-rich H4S, H5S, and H6S are
unstable in the pressure range we studied. Therefore, H2S sample with Tc 190 K at
high pressure might decompose to mixture H3S and S. Our finding resolve the debate
about the pressure-induced decomposition of H2S for a long time. Further
experimental studies of H2S and pure H3S at high pressure are still greatly demanded.
Acknowledgements
This work was supported by the National Basic Research Program of China (No.
2011CB808200), Program for Changjiang Scholars and Innovative Research Team in
University (No. IRT1132), National Natural Science Foundation of China (Nos.
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51032001, 11204100, 11074090, 10979001, 51025206, and 11104102), National
Found for Fostering Talents of basic Science (No. J1103202), Specialized Research
Fund for the Doctoral Program of Higher Education (20120061120008 and
20110061120007), and China Postdoctoral Science Foundation (2012M511326 and
2013T60314). Parts of calculations were performed in the High Performance
Computing Center (HPCC) of Jilin University.
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Fig. 1 | Chemical stabilities of stoichiometric HnS (n> 1) hydrides under pressure.
Predicted formation enthalpy of HnS with respect to decomposition into S and H2
under pressure. Dashed lines connect data points, and solid lines denote the convex
hull.
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Fig. 2 | Predicted pressure-composition phase diagram of stoichiometric HnS
(n>1) hydrides.
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Fig. 3 | Stable structures of H2S and H3S stoichiometries. a, H2S at 20 GPa in a P2c
structure. b, H2S at 40 GPa in a Pc structure. c, H3S at 20 GPa in a P1 structure. d,
H3S at 60 GPa in a Cccm structure. e, H3S at 130 GPa in a R-3m structure. f, H3S at
200 GPa in a Im-3m structure.
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Fig. 4 | Selected metastable structures of H4S, H5S and H6S stoichiometries. a,
H4S at 200 GPa in a Fmmm structure. b, H4S at 200 GPa in a Fmmm structure. c, H6S
at 200 GPa in a Cmma structure. d, H6S at 300 GPa in a Pbcn structure.