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Title: Hydrogen sulfide at high pressure: Change in stoichiometry

Abstract

Hydrogen sulfide (H2S) was studied by x-ray synchrotron diffraction and Raman spectroscopy up to 150 GPa at 180–295 K and by quantum-mechanical variable-composition evolutionary simulations. The experiments show that H2S becomes unstable with respect to formation of compounds with different structure and composition, including Cccm and a body-centered cubic like (R3m or Im – 3m) H3S, the latter one predicted previously to show a record-high superconducting transition temperature, a Tc of 203 K. Furthermore, these experiments provide experimental ground for understanding of this record-high Tc. The experimental results are supported by theoretical structure searches that suggest the stability of H3S, H4S3, H5S8, H3S5, and HS2 compounds that have not been reported previously at elevated pressures.

Authors:
 [1];  [2];  [3];  [4];  [5];  [6];  [7];  [8]
  1. Chinese Academy of Sciences, Anhui (China); Carnegie Inst. of Washington, Argonne, IL (United States); Univ. of Science and Technology of China, Hefei (China)
  2. Carnegie Inst. of Washington, Argonne, IL (United States); V. S. Sobolev Institute of Geology and Mineralogy, Novosibirsk (Russia)
  3. Moscow Inst. of Physics and Technology (Russia); All-Russia Research Institute of Automatics, Moscow (Russia)
  4. Carnegie Inst. of Washington, Argonne, IL (United States); South China Univ. of Technology, Guangzhou (China); Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
  5. Chinese Academy of Sciences, Anhui (China); Carnegie Inst. of Washington, Argonne, IL (United States); Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
  6. Moscow Inst. of Physics and Technology (Russia); All-Russia Research Institute of Automatics, Moscow (Russia); Skolkovo Inst. of Science and Technology, Moscow (Russia); State Univ. of New York, Stony Brook, NY (United States); Northwestern Polytechnical Univ., Xi'an (China)
  7. Deutsches Elektronen-Synchrotron (DESY), Hamburg (Germany)
  8. Univ. of Chicago, IL (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Defense Advanced Research Projects Agency (DARPA); Ministry of Education and Science of Russian Federation; ARO; NSFC
OSTI Identifier:
1253790
Alternate Identifier(s):
OSTI ID: 1252349
Grant/Contract Number:  
AC02-06CH11357; AC02-98CH10086; EAR-1114313; B08040; DMR-1231586; W31P4Q1210008; W31P4Q1310005; 14.B25.31.0032; W911NF-13-1-0231; EAR-152064; 1531583; 21473211; FG02-94ER14466
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 93; Journal Issue: 17; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
ENGLISH
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; composition; phase diagrams; pressure effects; superconducting gap; high-temperature superconductors; superconductors; Raman spectroscopy; X-ray scattering; condensed matter & materials physics

Citation Formats

Goncharov, Alexander F., Lobanov, Sergey S., Kruglov, Ivan, Zhao, Xiao-Miao, Chen, Xiao-Jia, Oganov, Artem R., Konôpková, Zuzana, and Prakapenka, Vitali B. Hydrogen sulfide at high pressure: Change in stoichiometry. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.93.174105.
Goncharov, Alexander F., Lobanov, Sergey S., Kruglov, Ivan, Zhao, Xiao-Miao, Chen, Xiao-Jia, Oganov, Artem R., Konôpková, Zuzana, & Prakapenka, Vitali B. Hydrogen sulfide at high pressure: Change in stoichiometry. United States. doi:10.1103/PhysRevB.93.174105.
Goncharov, Alexander F., Lobanov, Sergey S., Kruglov, Ivan, Zhao, Xiao-Miao, Chen, Xiao-Jia, Oganov, Artem R., Konôpková, Zuzana, and Prakapenka, Vitali B. Tue . "Hydrogen sulfide at high pressure: Change in stoichiometry". United States. doi:10.1103/PhysRevB.93.174105. https://www.osti.gov/servlets/purl/1253790.
@article{osti_1253790,
title = {Hydrogen sulfide at high pressure: Change in stoichiometry},
author = {Goncharov, Alexander F. and Lobanov, Sergey S. and Kruglov, Ivan and Zhao, Xiao-Miao and Chen, Xiao-Jia and Oganov, Artem R. and Konôpková, Zuzana and Prakapenka, Vitali B.},
abstractNote = {Hydrogen sulfide (H2S) was studied by x-ray synchrotron diffraction and Raman spectroscopy up to 150 GPa at 180–295 K and by quantum-mechanical variable-composition evolutionary simulations. The experiments show that H2S becomes unstable with respect to formation of compounds with different structure and composition, including Cccm and a body-centered cubic like (R3m or Im – 3m) H3S, the latter one predicted previously to show a record-high superconducting transition temperature, a Tc of 203 K. Furthermore, these experiments provide experimental ground for understanding of this record-high Tc. The experimental results are supported by theoretical structure searches that suggest the stability of H3S, H4S3, H5S8, H3S5, and HS2 compounds that have not been reported previously at elevated pressures.},
doi = {10.1103/PhysRevB.93.174105},
journal = {Physical Review B},
number = 17,
volume = 93,
place = {United States},
year = {2016},
month = {5}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

High-pressure phase of solid hydrogen sulfide
journal, July 1996


Quantum hydrogen-bond symmetrization in the superconducting hydrogen sulfide system
journal, March 2016

  • Errea, Ion; Calandra, Matteo; Pickard, Chris J.
  • Nature, Vol. 532, Issue 7597
  • DOI: 10.1038/nature17175

Molecular Dissociation in Deuterium Sulfide under High Pressure:  Infrared and Raman Study
journal, September 2000

  • Sakashita, Mami; Fujihisa, H.; Yamawaki, H.
  • The Journal of Physical Chemistry A, Vol. 104, Issue 38
  • DOI: 10.1021/jp001625m

High-pressure phase transitions of solid H 2 S probed by Fourier-transform infrared spectroscopy
journal, March 1997


Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Synchrotron infrared spectroscopy at megabar pressures: Vibrational dynamics of hydrogen to 180 GPa
journal, August 1992


New developments in evolutionary structure prediction algorithm USPEX
journal, April 2013

  • Lyakhov, Andriy O.; Oganov, Artem R.; Stokes, Harold T.
  • Computer Physics Communications, Vol. 184, Issue 4
  • DOI: 10.1016/j.cpc.2012.12.009

First-principles study of the pressure and crystal-structure dependences of the superconducting transition temperature in compressed sulfur hydrides
journal, June 2015


The metallization and superconductivity of dense hydrogen sulfide
journal, May 2014

  • Li, Yinwei; Hao, Jian; Liu, Hanyu
  • The Journal of Chemical Physics, Vol. 140, Issue 17
  • DOI: 10.1063/1.4874158

A little bit of lithium does a lot for hydrogen
journal, October 2009

  • Zurek, E.; Hoffmann, R.; Ashcroft, N. W.
  • Proceedings of the National Academy of Sciences, Vol. 106, Issue 42
  • DOI: 10.1073/pnas.0908262106

Pressure-Induced Molecular Dissociation and Metallization in Hydrogen-Bonded H 2 S Solid
journal, August 1997


Molecular dissociation and two low-temperature high-pressure phases of H 2 S
journal, June 2004


Dissociation products and structures of solid H 2 S at strong compression
journal, January 2016


Novel Cooperative Interactions and Structural Ordering in H 2 S H 2
journal, December 2011


Pressure-induced decomposition of solid hydrogen sulfide
journal, May 2015


Superconductivity in Hydrogen Dominant Materials: Silane
journal, March 2008


Ab initio Simulation of Phase Transitions and Dissociation of H 2 S at High Pressure
journal, August 2000


Crystal structure of the superconducting phases of S and Se
journal, June 2005


Hydrogen Dominant Metallic Alloys: High Temperature Superconductors?
journal, May 2004


Structures of H2S Phases I and IV under high pressure
journal, February 1998

  • Fujihisa, H.; Yamawaki, H.; Sakashita, M.
  • Physical Review B, Vol. 57, Issue 5, p. 2651-2654
  • DOI: 10.1103/PhysRevB.57.2651

Pressure-induced metallization of dense (H2S)2H2 with high-Tc superconductivity
journal, November 2014

  • Duan, Defang; Liu, Yunxian; Tian, Fubo
  • Scientific Reports, Vol. 4, Issue 1
  • DOI: 10.1038/srep06968

Conventional superconductivity at 203 kelvin at high pressures in the sulfur hydride system
journal, August 2015

  • Drozdov, A. P.; Eremets, M. I.; Troyan, I. A.
  • Nature, Vol. 525, Issue 7567
  • DOI: 10.1038/nature14964

Synthesis of lithium polyhydrides above 130 GPa at 300 K
journal, June 2015

  • Pépin, Charles; Loubeyre, Paul; Occelli, Florent
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 25
  • DOI: 10.1073/pnas.1507508112

How Evolutionary Crystal Structure Prediction Works—and Why
journal, March 2011

  • Oganov, Artem R.; Lyakhov, Andriy O.; Valle, Mario
  • Accounts of Chemical Research, Vol. 44, Issue 3
  • DOI: 10.1021/ar1001318

What superconducts in sulfur hydrides under pressure and why
journal, February 2015


High-Pressure Hydrogen Sulfide from First Principles: A Strongly Anharmonic Phonon-Mediated Superconductor
journal, April 2015


Evolutionary Crystal Structure Prediction as a Method for the Discovery of Minerals and Materials
journal, January 2010

  • Oganov, A. R.; Ma, Y.; Lyakhov, A. O.
  • Reviews in Mineralogy and Geochemistry, Vol. 71, Issue 1
  • DOI: 10.2138/rmg.2010.71.13

Crystal structure prediction using ab initio evolutionary techniques: Principles and applications
journal, June 2006

  • Oganov, Artem R.; Glass, Colin W.
  • The Journal of Chemical Physics, Vol. 124, Issue 24
  • DOI: 10.1063/1.2210932

High temperature superconductivity in sulfur and selenium hydrides at high pressure
journal, March 2016

  • Flores-Livas, José A.; Sanna, Antonio; Gross, E. K. U.
  • The European Physical Journal B, Vol. 89, Issue 3
  • DOI: 10.1140/epjb/e2016-70020-0

Raman Spectroscopy of Dense H 2 O and the Transition to Symmetric Hydrogen Bonds
journal, September 1999

  • Goncharov, Alexander F.; Struzhkin, Viktor V.; Mao, Ho-kwang
  • Physical Review Letters, Vol. 83, Issue 10
  • DOI: 10.1103/PhysRevLett.83.1998

    Works referencing / citing this record:

    Hydrogen sulfide at high pressure: Change in stoichiometry
    text, January 2016

    • Goncharov, Alexander; Lobanov, Sergey S.; Kruglov, Ivan
    • Deutsches Elektronen-Synchrotron, DESY, Hamburg
    • DOI: 10.3204/pubdb-2019-01795