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Title: Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces

Abstract

Here we report that an accurate understanding of the phase diagram of dense hydrogen and helium mixtures is a crucial component in the construction of accurate models of Jupiter, Saturn, and Jovian extrasolar planets. Though density-functional-theory-based first-principles methods have the potential to provide the accuracy and computational efficiency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quantification of the errors introduced. In this work, we present a quantum Monte Carlo (QMC) -based benchmarking study of a wide range of density functionals for use in hydrogen-helium mixtures at thermodynamic conditions relevant for Jovian planets. Not only do we continue our program of benchmarking energetics and pressures, but we deploy QMC-based force estimators and use them to gain insight into how well the local liquid structure is captured by different density functionals. We find that TPSS, BLYP, and vdW-DF are the most accurate functionals by most metrics, and that the enthalpy, energy, and pressure errors are very well behaved as a function of helium concentration. Beyond this, we highlight and analyze the major error trends and relative differences exhibited by the major classes of functionals, and we estimatemore » the magnitudes of these effects when possible.« less

Authors:
 [1];  [2];  [3];  [4]
  1. Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Physics; Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
  2. Univ. of Grenoble (France)
  3. Univ. of Illinois, Urbana-Champaign, IL (United States). Dept. of Physics
  4. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Univ. of Illinois, Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1325453
Alternate Identifier(s):
OSTI ID: 1235751; OSTI ID: 1358610
Grant/Contract Number:  
AC05-00OR22725; AC52-07NA27344; NA0001789; NA0002911
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 93; Journal Issue: 3; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats

Clay, Raymond C., Holzmann, Markus, Ceperley, David M., and Morales, Miguel A. Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces. United States: N. p., 2016. Web. doi:10.1103/PhysRevB.93.035121.
Clay, Raymond C., Holzmann, Markus, Ceperley, David M., & Morales, Miguel A. Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces. United States. doi:10.1103/PhysRevB.93.035121.
Clay, Raymond C., Holzmann, Markus, Ceperley, David M., and Morales, Miguel A. Tue . "Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces". United States. doi:10.1103/PhysRevB.93.035121. https://www.osti.gov/servlets/purl/1325453.
@article{osti_1325453,
title = {Benchmarking density functionals for hydrogen-helium mixtures with quantum Monte Carlo: Energetics, pressures, and forces},
author = {Clay, Raymond C. and Holzmann, Markus and Ceperley, David M. and Morales, Miguel A.},
abstractNote = {Here we report that an accurate understanding of the phase diagram of dense hydrogen and helium mixtures is a crucial component in the construction of accurate models of Jupiter, Saturn, and Jovian extrasolar planets. Though density-functional-theory-based first-principles methods have the potential to provide the accuracy and computational efficiency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quantification of the errors introduced. In this work, we present a quantum Monte Carlo (QMC) -based benchmarking study of a wide range of density functionals for use in hydrogen-helium mixtures at thermodynamic conditions relevant for Jovian planets. Not only do we continue our program of benchmarking energetics and pressures, but we deploy QMC-based force estimators and use them to gain insight into how well the local liquid structure is captured by different density functionals. We find that TPSS, BLYP, and vdW-DF are the most accurate functionals by most metrics, and that the enthalpy, energy, and pressure errors are very well behaved as a function of helium concentration. Beyond this, we highlight and analyze the major error trends and relative differences exhibited by the major classes of functionals, and we estimate the magnitudes of these effects when possible.},
doi = {10.1103/PhysRevB.93.035121},
journal = {Physical Review B},
number = 3,
volume = 93,
place = {United States},
year = {2016},
month = {1}
}

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    Works referencing / citing this record:

    Quantum Monte Carlo assessment of density functionals for π -electron molecules: ethylene and bifuran
    journal, August 2018