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Title: Structure and Metallicity of Phase V of Hydrogen

Abstract

A new phase V of hydrogen was recently claimed in experiments above 325 GPa and 300 K. Because of the extremely small sample size at such record pressures the measurements were limited to Raman spectroscopy. The experimental data on increase of pressure show decreasing Raman activity and darkening of the sample, which suggests band gap closure and impending molecular dissociation, but no definite conclusions could be reached. Furthermore, the available data are insufficient to determine the structure of phase V, which remains unknown. Introducing saddle-point ab initio random structure searching, we find several new structural candidates of hydrogen which could describe the observed properties of phase V. We investigate hydrogen metallization in the proposed candidate structures, and demonstrate that smaller band gaps are associated with longer bond lengths. We conclude that phase V is a stepping stone towards metallization.

Authors:
 [1];  [2];  [3];  [3];  [4];  [5];  [6];  [7]
  1. Rutgers Univ., Piscataway, NJ (United States); Univ. of Cambridge (United Kingdom). Cavendish Lab.
  2. Lancaster Univ. (United Kingdom). Dept. of Physics
  3. Center for High Pressure Science and Technology Advanced Research, Shanghai (China)
  4. Univ. of Cambridge (United Kingdom). Cavendish Lab.; Max Planck Inst. for Solid State Research, Stuttgart (Germany)
  5. Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Univ. of Edinburgh, Scotland (United Kingdom). Centre for Science at Extreme Conditions and School of Physics and Astronomy,; Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Remote Sensing and Digital Earth, Key Lab. of Materials Physics
  6. Univ. of Cambridge (United Kingdom). Dept. of Materials Science and Metallurgy; Tohoku Univ., Sendai (Japan). WPI-Advanced Inst. for Materials Research
  7. Univ. of Cambridge (United Kingdom). Cavendish Lab.
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); UT-Battelle LLC/ORNL, Oak Ridge, TN (Unted States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1565692
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 120; Journal Issue: 25; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
Physics

Citation Formats

Monserrat, Bartomeu, Drummond, Neil D., Dalladay-Simpson, Philip, Howie, Ross T., López Ríos, Pablo, Gregoryanz, Eugene, Pickard, Chris J., and Needs, Richard J. Structure and Metallicity of Phase V of Hydrogen. United States: N. p., 2018. Web. doi:10.1103/physrevlett.120.255701.
Monserrat, Bartomeu, Drummond, Neil D., Dalladay-Simpson, Philip, Howie, Ross T., López Ríos, Pablo, Gregoryanz, Eugene, Pickard, Chris J., & Needs, Richard J. Structure and Metallicity of Phase V of Hydrogen. United States. doi:10.1103/physrevlett.120.255701.
Monserrat, Bartomeu, Drummond, Neil D., Dalladay-Simpson, Philip, Howie, Ross T., López Ríos, Pablo, Gregoryanz, Eugene, Pickard, Chris J., and Needs, Richard J. Fri . "Structure and Metallicity of Phase V of Hydrogen". United States. doi:10.1103/physrevlett.120.255701.
@article{osti_1565692,
title = {Structure and Metallicity of Phase V of Hydrogen},
author = {Monserrat, Bartomeu and Drummond, Neil D. and Dalladay-Simpson, Philip and Howie, Ross T. and López Ríos, Pablo and Gregoryanz, Eugene and Pickard, Chris J. and Needs, Richard J.},
abstractNote = {A new phase V of hydrogen was recently claimed in experiments above 325 GPa and 300 K. Because of the extremely small sample size at such record pressures the measurements were limited to Raman spectroscopy. The experimental data on increase of pressure show decreasing Raman activity and darkening of the sample, which suggests band gap closure and impending molecular dissociation, but no definite conclusions could be reached. Furthermore, the available data are insufficient to determine the structure of phase V, which remains unknown. Introducing saddle-point ab initio random structure searching, we find several new structural candidates of hydrogen which could describe the observed properties of phase V. We investigate hydrogen metallization in the proposed candidate structures, and demonstrate that smaller band gaps are associated with longer bond lengths. We conclude that phase V is a stepping stone towards metallization.},
doi = {10.1103/physrevlett.120.255701},
journal = {Physical Review Letters},
issn = {0031-9007},
number = 25,
volume = 120,
place = {United States},
year = {2018},
month = {6}
}

Works referenced in this record:

Metallic Hydrogen: A High-Temperature Superconductor?
journal, December 1968


The solid molecular hydrogens in the condensed phase: Fundamentals and static properties
journal, April 1980


The properties of hydrogen and helium under extreme conditions
journal, November 2012

  • McMahon, Jeffrey M.; Morales, Miguel A.; Pierleoni, Carlo
  • Reviews of Modern Physics, Vol. 84, Issue 4
  • DOI: 10.1103/RevModPhys.84.1607

Hydrogen at extreme pressures (Review Article)
journal, May 2013

  • Goncharov, Alexander F.; Howie, Ross T.; Gregoryanz, Eugene
  • Low Temperature Physics, Vol. 39, Issue 5
  • DOI: 10.1063/1.4807051

On the Possibility of a Metallic Modification of Hydrogen
journal, December 1935

  • Wigner, E.; Huntington, H. B.
  • The Journal of Chemical Physics, Vol. 3, Issue 12
  • DOI: 10.1063/1.1749590

New Low-Temperature Phase of Molecular Deuterium at Ultrahigh Pressure
journal, July 1981


Phase Transition in Solid Molecular Hydrogen at Ultrahigh Pressures
journal, August 1988


Conductive dense hydrogen
journal, November 2011

  • Eremets, M. I.; Troyan, I. A.
  • Nature Materials, Vol. 10, Issue 12
  • DOI: 10.1038/nmat3175

Mixed Molecular and Atomic Phase of Dense Hydrogen
journal, March 2012


Proton tunneling in phase IV of hydrogen and deuterium
journal, December 2012


Structure of phase III of solid hydrogen
journal, May 2007

  • Pickard, Chris J.; Needs, Richard J.
  • Nature Physics, Vol. 3, Issue 7
  • DOI: 10.1038/nphys625

High-temperature superconductivity in atomic metallic hydrogen
journal, October 2011


Density functional theory study of phase IV of solid hydrogen
journal, June 2012

  • Pickard, Chris J.; Martinez-Canales, Miguel; Needs, Richard J.
  • Physical Review B, Vol. 85, Issue 21
  • DOI: 10.1103/PhysRevB.85.214114

Erratum: Density functional theory study of phase IV of solid hydrogen [Phys. Rev. B 85 , 214114 (2012)]
journal, August 2012

  • Pickard, Chris J.; Martinez-Canales, Miguel; Needs, Richard J.
  • Physical Review B, Vol. 86, Issue 5
  • DOI: 10.1103/PhysRevB.86.059902

Room-temperature structures of solid hydrogen at high pressures
journal, August 2012

  • Liu, Hanyu; Zhu, Li; Cui, Wenwen
  • The Journal of Chemical Physics, Vol. 137, Issue 7
  • DOI: 10.1063/1.4745186

Identification of high-pressure phases III and IV in hydrogen: Simulating Raman spectra using molecular dynamics
journal, May 2013


Dissociation of High-Pressure Solid Molecular Hydrogen: A Quantum Monte Carlo and Anharmonic Vibrational Study
journal, April 2014


Molecular to Atomic Phase Transition in Hydrogen under High Pressure
journal, March 2015


Quantum Monte Carlo study of the phase diagram of solid molecular hydrogen at extreme pressures
journal, July 2015

  • Drummond, N. D.; Monserrat, Bartomeu; Lloyd-Williams, Jonathan H.
  • Nature Communications, Vol. 6, Issue 1
  • DOI: 10.1038/ncomms8794

Evidence for a new phase of dense hydrogen above 325 gigapascals
journal, January 2016

  • Dalladay-Simpson, Philip; Howie, Ross T.; Gregoryanz, Eugene
  • Nature, Vol. 529, Issue 7584
  • DOI: 10.1038/nature16164

Observation of the Wigner-Huntington transition to metallic hydrogen
journal, January 2017


Comment on “Observation of the Wigner-Huntington transition to metallic hydrogen”
journal, August 2017

  • Liu, Xiao-Di; Dalladay-Simpson, Philip; Howie, Ross T.
  • Science, Vol. 357, Issue 6353
  • DOI: 10.1126/science.aan2286

Comment on “Observation of the Wigner-Huntington transition to metallic hydrogen”
journal, August 2017


Hexagonal structure of phase III of solid hydrogen
journal, October 2016


High-Pressure Phases of Silane
journal, July 2006


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

Crystal structure prediction via particle-swarm optimization
journal, September 2010


Ab initio random structure searching
journal, January 2011


XtalOpt: An open-source evolutionary algorithm for crystal structure prediction
journal, February 2011


Lattice instabilities in metallic elements
journal, June 2012

  • Grimvall, Göran; Magyari-Köpe, Blanka; Ozoliņš, Vidvuds
  • Reviews of Modern Physics, Vol. 84, Issue 2
  • DOI: 10.1103/RevModPhys.84.945

Phase Transitions in BaTi O 3 from First Principles
journal, September 1994


Studies in Molecular Dynamics. I. General Method
journal, August 1959

  • Alder, B. J.; Wainwright, T. E.
  • The Journal of Chemical Physics, Vol. 31, Issue 2
  • DOI: 10.1063/1.1730376

Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


The formulation of quantum statistical mechanics based on the Feynman path centroid density. I. Equilibrium properties
journal, April 1994

  • Cao, Jianshu; Voth, Gregory A.
  • The Journal of Chemical Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.467175

The formulation of quantum statistical mechanics based on the Feynman path centroid density. II. Dynamical properties
journal, April 1994

  • Cao, Jianshu; Voth, Gregory A.
  • The Journal of Chemical Physics, Vol. 100, Issue 7
  • DOI: 10.1063/1.467176

Entropy Driven Stabilization of Energetically Unstable Crystal Structures Explained from First Principles Theory
journal, March 2008


Lattice dynamics of anharmonic solids from first principles
journal, November 2011


Fast free-energy calculations for unstable high-temperature phases
journal, August 2012


Anharmonic vibrational properties in periodic systems: energy, electron-phonon coupling, and stress
journal, April 2013


Benchmarking exchange-correlation functionals for hydrogen at high pressures using quantum Monte Carlo
journal, May 2014


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

Fate of density functional theory in the study of high-pressure solid hydrogen
journal, July 2013


Continuum variational and diffusion quantum Monte Carlo calculations
journal, December 2009


Lattice dynamics and electron-phonon coupling calculations using nondiagonal supercells
journal, November 2015


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Vibrational wave functions and spectroscopy of (H 2 O) n , n =2,3,4,5: Vibrational self‐consistent field with correlation corrections
journal, December 1996

  • Jung, Joon O.; Gerber, R. Benny
  • The Journal of Chemical Physics, Vol. 105, Issue 23
  • DOI: 10.1063/1.472960

Self‐consistent field energies and wavefunctions for coupled oscillators
journal, January 1978

  • Bowman, Joel M.
  • The Journal of Chemical Physics, Vol. 68, Issue 2
  • DOI: 10.1063/1.435782

Quantum Monte Carlo simulations of solids
journal, January 2001


Twist-averaged boundary conditions in continuum quantum Monte Carlo algorithms
journal, June 2001


Quantum Monte Carlo study of high pressure solid molecular hydrogen
journal, November 2013


Towards a predictive first-principles description of solid molecular hydrogen with density functional theory
journal, May 2013


Nuclear quantum effects induce metallization of dense solid molecular hydrogen
journal, November 2017

  • Azadi, Sam; Singh, Ranber; Kühne, Thomas D.
  • Journal of Computational Chemistry, Vol. 39, Issue 5
  • DOI: 10.1002/jcc.25104

Electronic excitations and metallization of dense solid hydrogen
journal, July 2013

  • Cohen, R. E.; Naumov, Ivan I.; Hemley, Russell J.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 34
  • DOI: 10.1073/pnas.1312256110