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Title: Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory

Abstract

Outstanding problems in the high-pressure phase diagram of hydrogen have demonstrated the need for more accurate ab initio methods for thermodynamic sampling. One promising method that has been deployed extensively above 100 GPa is coupled electron-ion Monte Carlo (CEIMC), which treats the electronic structure with quantum Monte Carlo (QMC). However, CEIMC predictions of the deuterium principal Hugoniot disagree significantly with experiment, overshooting the experimentally determined peak compression density by 7% and lower temperature gas-gun data by well over 20%. By deriving an equation relating the predicted Hugoniot density to underlying equation of state errors, we show that QMC and many-body methods can easily spoil the error cancellation properties inherent in the Rankine-Hugoniot relation, and very likely suffer from error addition. By cross validating QMC based on systematically improvable trial functions against post-Hartree-Fock many-body methods, we find that these methods introduce errors of the right sign and magnitude to account for much of the observed discrepancy between CEIMC and experiment. In conclusion, we stress that this is not just a CEIMC problem, but that thermodynamic sampling based on other many-body methods is likely to experience similar difficulties.

Authors:
 [1];  [1];  [1]
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  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Pulsed Power Sciences Center
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1574698
Alternate Identifier(s):
OSTI ID: 1546843
Report Number(s):
SAND-2019-9668J
Journal ID: ISSN 2469-9950; PRBMDO; 678577; TRN: US2100094
Grant/Contract Number:  
AC04-94AL85000; NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 100; Journal Issue: 7; 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

Citation Formats

Clay, III, Raymond C., Desjarlais, Michael P., and Shulenburger, Luke. Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory. United States: N. p., 2019. Web. doi:10.1103/PhysRevB.100.075103.
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Clay, III, Raymond C., Desjarlais, Michael P., & Shulenburger, Luke. Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory. United States. https://doi.org/10.1103/PhysRevB.100.075103
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Clay, III, Raymond C., Desjarlais, Michael P., and Shulenburger, Luke. Thu . "Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory". United States. https://doi.org/10.1103/PhysRevB.100.075103. https://www.osti.gov/servlets/purl/1574698.
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@article{osti_1574698,
title = {Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory},
author = {Clay, III, Raymond C. and Desjarlais, Michael P. and Shulenburger, Luke},
abstractNote = {Outstanding problems in the high-pressure phase diagram of hydrogen have demonstrated the need for more accurate ab initio methods for thermodynamic sampling. One promising method that has been deployed extensively above 100 GPa is coupled electron-ion Monte Carlo (CEIMC), which treats the electronic structure with quantum Monte Carlo (QMC). However, CEIMC predictions of the deuterium principal Hugoniot disagree significantly with experiment, overshooting the experimentally determined peak compression density by 7% and lower temperature gas-gun data by well over 20%. By deriving an equation relating the predicted Hugoniot density to underlying equation of state errors, we show that QMC and many-body methods can easily spoil the error cancellation properties inherent in the Rankine-Hugoniot relation, and very likely suffer from error addition. By cross validating QMC based on systematically improvable trial functions against post-Hartree-Fock many-body methods, we find that these methods introduce errors of the right sign and magnitude to account for much of the observed discrepancy between CEIMC and experiment. In conclusion, we stress that this is not just a CEIMC problem, but that thermodynamic sampling based on other many-body methods is likely to experience similar difficulties.},
doi = {10.1103/PhysRevB.100.075103},
journal = {Physical Review B},
number = 7,
volume = 100,
place = {United States},
year = {Thu Aug 01 00:00:00 EDT 2019},
month = {Thu Aug 01 00:00:00 EDT 2019}
}
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https://doi.org/10.1103/PhysRevB.100.075103
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Cited by: 5 works
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Figures / Tables:

FIG. 1 FIG. 1: Pressure vs. density compression of the principal deuterium Hugoniot. Diamonds are the experimental data from Refs.28,29, filled circles are the published CEIMC data, and hollow circles are the corrected CEIMC Hugoniot points using methods in this paper. PW91 and vdW-DF Hugoniots from Ref.28 included for comparison.
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