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

Journal Article · · Physical Review B
 [1];  [2];  [3];  [4]
  1. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Univ. of Illinois, Urbana-Champaign, IL (United States)
  2. Univ. Grenobles Alpes (France). LPMMC
  3. Univ. of Illinois, Urbana-Champaign, IL (United States)
  4. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
+ Show Author Affiliations

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 DFT based rst principles methods have the potential to provide the accuracy and computational e ciency required for this task, recent benchmarking in hydrogen has shown that achieving this accuracy requires a judicious choice of functional, and a quanti cation of the errors introduced. In this work, we present a quantum Monte Carlo 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 insights into how well the local liquid structure is captured by di erent density functionals. We nd 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 di erences exhibited by the major classes of functionals, and estimate the magnitudes of these e ects when possible.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Organization:
DOE Office of Science; USDOE
Grant/Contract Number:
AC52-07NA27344; AC05-00OR22725; NA0001789
OSTI ID:
1241957
Report Number(s):
LLNL--JRNL-676457
Journal Information:
Physical Review B, Journal Name: Physical Review B Journal Issue: 3 Vol. 93; ISSN 2469-9950
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (11)

Nuclear quantum effects induce metallization of dense solid molecular hydrogen journal November 2017
Extent of Fock-exchange mixing for a hybrid van der Waals density functional? journal May 2018
Quantum Monte Carlo assessment of density functionals for π -electron molecules: ethylene and bifuran journal August 2018
QMCPACK : an open source ab initio quantum Monte Carlo package for the electronic structure of atoms, molecules and solids journal April 2018
Theory of finite size effects for electronic quantum Monte Carlo calculations of liquids and solids journal July 2016
First-principles prediction of the softening of the silicon shock Hugoniot curve journal September 2016
Quantum molecular dynamics study on the proton exchange, ionic structures, and transport properties of warm dense hydrogen-deuterium mixtures journal June 2018
Ab Initio Calculation of the Miscibility Diagram for Hydrogen-Helium Mixtures journal March 2018
Nuclear Quantum Effects Induce Metallization of Dense Solid Molecular Hydrogen preprint January 2017
QMCPACK : An open source ab initio Quantum Monte Carlo package for the electronic structure of atoms, molecules, and solids text January 2018
Extent of Fock-exchange mixing for a hybrid van der Waals density functional? text January 2018

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