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Title: Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional

Abstract

For orbital-free ab initio molecular dynamics, especially on systems in extreme thermodynamic conditions, we provide the first pseudo-potential-adapted generalized gradient approximation (GGA) functional for the non-interacting free energy. This is achieved by systematic finite-temperature extension of our recent LKT ground state non-interacting kinetic energy GGA functional (Phys. Rev. B 98, 041111(R) (2018)). We test the performance of the new functional first via static lattice calculations on crystalline aluminum and silicon. Then we compare deuterium equation of state results against both path-integral Monte Carlo and conventional (orbital-dependent) Kohn-Sham results. The new functional, denoted LKTF, outperforms the previous best semi-local free energy functional, VT84F (Phys. Rev. B 88, 161108(R) (2013)), and provides modestly faster simulations. Finally, we discuss subtleties of identification of kinetic and entropic contributions to non-interacting free-energy functionals obtained by extension from ground state orbital-free kinetic energy functionals.

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3]
  1. Carnegie Inst. of Washington, Washington, DC (United States)
  2. Univ. of Rochester, NY (United States)
  3. Univ. of Florida, Gainesville, FL (United States)
Publication Date:
Research Org.:
Univ. of Rochester, NY (United States); Univ. of Florida, Gainesville, FL (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1602230
Alternate Identifier(s):
OSTI ID: 1599503
Report Number(s):
2020-42; 1549
Journal ID: ISSN 2469-9950; PRBMDO; 2020-42, 2506, 1549
Grant/Contract Number:  
NA0003856; SC0002139; NA0001944
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review B
Additional Journal Information:
Journal Volume: 101; Journal Issue: 7; 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; warm-dense matter; density functional theory development; GGA

Citation Formats

Luo, K., Karasiev, V. V., and Trickey, S. B. Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional. United States: N. p., 2020. Web. doi:10.1103/PhysRevB.101.075116.
Luo, K., Karasiev, V. V., & Trickey, S. B. Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional. United States. doi:https://doi.org/10.1103/PhysRevB.101.075116
Luo, K., Karasiev, V. V., and Trickey, S. B. Thu . "Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional". United States. doi:https://doi.org/10.1103/PhysRevB.101.075116. https://www.osti.gov/servlets/purl/1602230.
@article{osti_1602230,
title = {Towards accurate orbital-free simulations: A generalized gradient approximation for the noninteracting free energy density functional},
author = {Luo, K. and Karasiev, V. V. and Trickey, S. B.},
abstractNote = {For orbital-free ab initio molecular dynamics, especially on systems in extreme thermodynamic conditions, we provide the first pseudo-potential-adapted generalized gradient approximation (GGA) functional for the non-interacting free energy. This is achieved by systematic finite-temperature extension of our recent LKT ground state non-interacting kinetic energy GGA functional (Phys. Rev. B 98, 041111(R) (2018)). We test the performance of the new functional first via static lattice calculations on crystalline aluminum and silicon. Then we compare deuterium equation of state results against both path-integral Monte Carlo and conventional (orbital-dependent) Kohn-Sham results. The new functional, denoted LKTF, outperforms the previous best semi-local free energy functional, VT84F (Phys. Rev. B 88, 161108(R) (2013)), and provides modestly faster simulations. Finally, we discuss subtleties of identification of kinetic and entropic contributions to non-interacting free-energy functionals obtained by extension from ground state orbital-free kinetic energy functionals.},
doi = {10.1103/PhysRevB.101.075116},
journal = {Physical Review B},
number = 7,
volume = 101,
place = {United States},
year = {2020},
month = {2}
}

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