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Deuterium Hugoniot: Pitfalls of thermodynamic sampling beyond density functional theory

Journal Article · · Physical Review B
 [1];  [1];  [1]
  1. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States). Pulsed Power Sciences Center
+ Show Author Affiliations
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.
Research Organization:
Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Sponsoring Organization:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Grant/Contract Number:
AC04-94AL85000; NA0003525
OSTI ID:
1574698
Alternate ID(s):
OSTI ID: 1546843
Report Number(s):
SAND--2019-9668J; 678577
Journal Information:
Physical Review B, Journal Name: Physical Review B Journal Issue: 7 Vol. 100; ISSN 2469-9950; ISSN PRBMDO
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

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Figures / Tables (12)

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75 CONDENSED MATTER PHYSICS
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