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Title: Evaluation of exchange-correlation functionals with multiple-shock conductivity measurements in hydrogen and deuterium at the molecular-to-atomic transition

Abstract

The temperature (T) and density (ρ) conditions at which hydrogen undergoes a molecular-to-atomic (MA) transition is crucial to our understanding of the gas-giant planets such as Jupiter and Saturn. First-principles (FP) calculations suggest that this transition is coincident with metallization and acts as a catalyst for hydrogen-helium demixing, which has significant consequences for models of planetary interiors. Prediction of this transition boundary has proven to be difficult using FP methods. In particular, detailed comparisons of finite temperature density functional theory (FT-DFT) calculations of the MA transition in both the high-T, low-ρ regime, where the transition is largely T driven, and the low-T, high-ρ regime, where the transition is largely ρ driven, suggest that the transition is very sensitive to the exchange-correlation (xc) functional used in the calculation. Here we present a detailed comparison of previous multiple-shock electrical conductivity measurements with FT-DFT calculations employing various xc functionals to probe a regime where both T and ρ play an important role in the transition. The measurement results are found to be inconsistent with the semilocal xc functional PBE and are in much better agreement with the nonlocal xc functionals vdW-DF1 and vdW-DF2. Furthermore, we show that the inconsistency with PBE likely stemsmore » from pressure errors associated with the PBE xc functional, resulting in calculated pressures that are too low at these T and ρ conditions. Together with previous comparisons at high-T, low-ρ and low-T, high-ρ these results provide a consistent picture for the MA transition over a wide T and ρ range. Here, this picture may also provide insight into differences in experimental observations of the metallization of liquid hydrogen and deuterium in the low-T regime.« less

Authors:
 [1];  [2];  [3];  [3]
  1. Washington State Univ., Pullman, WA (United States); Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
  3. Univ. of Rostock, Rostock (Germany)
Publication Date:
Research Org.:
Washington State Univ., Pullman, WA (United States). Inst. for Shock Physics
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA), Office of Defense Programs (DP)
OSTI Identifier:
1493764
Alternate Identifier(s):
OSTI ID: 1492145
Grant/Contract Number:  
NA0002007; NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 98; 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; 08 HYDROGEN

Citation Formats

Knudson, M. D., Desjarlais, M. P., Preising, M., and Redmer, R. Evaluation of exchange-correlation functionals with multiple-shock conductivity measurements in hydrogen and deuterium at the molecular-to-atomic transition. United States: N. p., 2018. Web. doi:10.1103/PhysRevB.98.174110.
Knudson, M. D., Desjarlais, M. P., Preising, M., & Redmer, R. Evaluation of exchange-correlation functionals with multiple-shock conductivity measurements in hydrogen and deuterium at the molecular-to-atomic transition. United States. doi:10.1103/PhysRevB.98.174110.
Knudson, M. D., Desjarlais, M. P., Preising, M., and Redmer, R. Mon . "Evaluation of exchange-correlation functionals with multiple-shock conductivity measurements in hydrogen and deuterium at the molecular-to-atomic transition". United States. doi:10.1103/PhysRevB.98.174110. https://www.osti.gov/servlets/purl/1493764.
@article{osti_1493764,
title = {Evaluation of exchange-correlation functionals with multiple-shock conductivity measurements in hydrogen and deuterium at the molecular-to-atomic transition},
author = {Knudson, M. D. and Desjarlais, M. P. and Preising, M. and Redmer, R.},
abstractNote = {The temperature (T) and density (ρ) conditions at which hydrogen undergoes a molecular-to-atomic (MA) transition is crucial to our understanding of the gas-giant planets such as Jupiter and Saturn. First-principles (FP) calculations suggest that this transition is coincident with metallization and acts as a catalyst for hydrogen-helium demixing, which has significant consequences for models of planetary interiors. Prediction of this transition boundary has proven to be difficult using FP methods. In particular, detailed comparisons of finite temperature density functional theory (FT-DFT) calculations of the MA transition in both the high-T, low-ρ regime, where the transition is largely T driven, and the low-T, high-ρ regime, where the transition is largely ρ driven, suggest that the transition is very sensitive to the exchange-correlation (xc) functional used in the calculation. Here we present a detailed comparison of previous multiple-shock electrical conductivity measurements with FT-DFT calculations employing various xc functionals to probe a regime where both T and ρ play an important role in the transition. The measurement results are found to be inconsistent with the semilocal xc functional PBE and are in much better agreement with the nonlocal xc functionals vdW-DF1 and vdW-DF2. Furthermore, we show that the inconsistency with PBE likely stems from pressure errors associated with the PBE xc functional, resulting in calculated pressures that are too low at these T and ρ conditions. Together with previous comparisons at high-T, low-ρ and low-T, high-ρ these results provide a consistent picture for the MA transition over a wide T and ρ range. Here, this picture may also provide insight into differences in experimental observations of the metallization of liquid hydrogen and deuterium in the low-T regime.},
doi = {10.1103/PhysRevB.98.174110},
journal = {Physical Review B},
number = 17,
volume = 98,
place = {United States},
year = {2018},
month = {11}
}

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Works referenced in this record:

Phase boundary of hot dense fluid hydrogen
journal, November 2015

  • Ohta, Kenji; Ichimaru, Kota; Einaga, Mari
  • Scientific Reports, Vol. 5, Issue 1
  • DOI: 10.1038/srep16560

High-Precision Shock Wave Measurements of Deuterium: Evaluation of Exchange-Correlation Functionals at the Molecular-to-Atomic Transition
journal, January 2017


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

Optical Properties of Fluid Hydrogen at the Transition to a Conducting State
journal, June 2016


A molecular dynamics method for simulations in the canonical ensemble
journal, June 1984


On Convection and Gravitational Layering in Jupiter and in Stars of Low Mass
journal, April 1973

  • Salpeter, E. E.
  • The Astrophysical Journal, Vol. 181
  • DOI: 10.1086/181190

Interiors of Giant Planets Inside and Outside the Solar System
journal, October 1999


Jupiter Models with Improved ab Initio Hydrogen Equation of State (H-Reos.2)
journal, April 2012


Higher-accuracy van der Waals density functional
journal, August 2010


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Magnetically launched flyer plate technique for probing electrical conductivity of compressed copper
journal, March 2016

  • Cochrane, K. R.; Lemke, R. W.; Riford, Z.
  • Journal of Applied Physics, Vol. 119, Issue 10
  • DOI: 10.1063/1.4943417

Insulator-metal transition of fluid molecular hydrogen
journal, October 1996


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
journal, May 1994


Direct observation of an abrupt insulator-to-metal transition in dense liquid deuterium
journal, June 2015


Evidence of a liquid-liquid phase transition in hot dense hydrogen
journal, April 2013

  • Dzyabura, V.; Zaghoo, M.; Silvera, I. F.
  • Proceedings of the National Academy of Sciences, Vol. 110, Issue 20
  • DOI: 10.1073/pnas.1300718110

Minimum metallic conductivity of fluid hydrogen at 140 GPa (1.4 Mbar)
journal, February 1999


Van der Waals Density Functional for General Geometries
journal, June 2004


Canonical dynamics: Equilibrium phase-space distributions
journal, March 1985


Structure and Phase Boundaries of Compressed Liquid Hydrogen
journal, February 2010


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

Conductivity and dissociation in liquid metallic hydrogen and implications for planetary interiors
journal, October 2017

  • Zaghoo, Mohamed; Silvera, Isaac F.
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 45
  • DOI: 10.1073/pnas.1707918114

Metallization in hydrogen-helium mixtures
journal, December 2011


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Metallization of Fluid Molecular Hydrogen at 140 GPa (1.4 Mbar)
journal, March 1996


Linear-mixing model for shock-compressed liquid deuterium
journal, July 1998


Diagnostic system of the Lawrence Livermore National Laboratory two‐stage light‐gas gun
journal, March 1981

  • Mitchell, A. C.; Nellis, W. J.
  • Review of Scientific Instruments, Vol. 52, Issue 3
  • DOI: 10.1063/1.1136602

Thermophysical properties of warm dense hydrogen using quantum molecular dynamics simulations
journal, May 2008


Evidence for a first-order liquid-liquid transition in high-pressure hydrogen from ab initio simulations
journal, June 2010

  • Morales, M. A.; Pierleoni, C.; Schwegler, E.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 29
  • DOI: 10.1073/pnas.1007309107

Nuclear Quantum Effects and Nonlocal Exchange-Correlation Functionals Applied to Liquid Hydrogen at High Pressure
journal, February 2013


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


A unified formulation of the constant temperature molecular dynamics methods
journal, July 1984

  • Nosé, Shuichi
  • The Journal of Chemical Physics, Vol. 81, Issue 1
  • DOI: 10.1063/1.447334

First-order liquid-liquid phase transition in dense hydrogen
journal, November 2010


Pulsed-power-driven high energy density physics and inertial confinement fusion research
journal, May 2005

  • Matzen, M. Keith; Sweeney, M. A.; Adams, R. G.
  • Physics of Plasmas, Vol. 12, Issue 5
  • DOI: 10.1063/1.1891746

Theoretical equation of state for aluminum
journal, January 1987


The Boltzmann Equation in the Theory of Electrical Conduction in Metals
journal, April 1958


Internal Structure and Energy Emission of Jupiter
journal, August 1967


Temperature measurements and dissociation of shock-compressed liquid deuterium and hydrogen
journal, December 1995


Multiphase equation of state of hydrogen from ab initio calculations in the range 0.2 to 5 g/cc up to 10 eV
journal, March 2011


Evidence of a first-order phase transition to metallic hydrogen
journal, April 2016


    Works referencing / citing this record:

    Plasma phase transition (by the fiftieth anniversary of the prediction)
    journal, March 2019

    • Norman, Genri E.; Saitov, Ilnur M.
    • Contributions to Plasma Physics, Vol. 59, Issue 6
    • DOI: 10.1002/ctpp.201800182

    Plasma phase transition (by the fiftieth anniversary of the prediction)
    journal, March 2019

    • Norman, Genri E.; Saitov, Ilnur M.
    • Contributions to Plasma Physics, Vol. 59, Issue 6
    • DOI: 10.1002/ctpp.201800182

    Metastable molecular fluid hydrogen at high pressures
    journal, April 2019

    • Norman, Genri E.; Saitov, Ilnur M.; Sartan, Roman A.
    • Contributions to Plasma Physics, Vol. 59, Issue 6
    • DOI: 10.1002/ctpp.201800173

    Benchmarking vdW-DF first-principles predictions against Coupled Electron-Ion Monte Carlo for high-pressure liquid hydrogen
    journal, February 2019

    • Gorelov, Vitaly; Pierleoni, Carlo; Ceperley, David M.
    • Contributions to Plasma Physics, Vol. 59, Issue 4-5
    • DOI: 10.1002/ctpp.201800185