Towards accurate orbitalfree simulations: A generalized gradient approximation for the noninteracting free energy density functional
Abstract
For orbitalfree ab initio molecular dynamics, especially on systems in extreme thermodynamic conditions, we provide the first pseudopotentialadapted generalized gradient approximation (GGA) functional for the noninteracting free energy. This is achieved by systematic finitetemperature extension of our recent LKT ground state noninteracting 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 pathintegral Monte Carlo and conventional (orbitaldependent) KohnSham results. The new functional, denoted LKTF, outperforms the previous best semilocal 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 noninteracting freeenergy functionals obtained by extension from ground state orbitalfree kinetic energy functionals.
 Authors:

 Carnegie Inst. of Washington, Washington, DC (United States)
 Univ. of Rochester, NY (United States)
 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):
 202042; 1549
Journal ID: ISSN 24699950; PRBMDO; 202042, 2506, 1549; TRN: US2103977
 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 24699950
 Publisher:
 American Physical Society (APS)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; warmdense matter; density functional theory development; GGA
Citation Formats
Luo, K., Karasiev, V. V., and Trickey, S. B. Towards accurate orbitalfree 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 orbitalfree simulations: A generalized gradient approximation for the noninteracting free energy density functional. United States. https://doi.org/10.1103/PhysRevB.101.075116
Luo, K., Karasiev, V. V., and Trickey, S. B. Thu .
"Towards accurate orbitalfree simulations: A generalized gradient approximation for the noninteracting free energy density functional". United States. https://doi.org/10.1103/PhysRevB.101.075116. https://www.osti.gov/servlets/purl/1602230.
@article{osti_1602230,
title = {Towards accurate orbitalfree 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 orbitalfree ab initio molecular dynamics, especially on systems in extreme thermodynamic conditions, we provide the first pseudopotentialadapted generalized gradient approximation (GGA) functional for the noninteracting free energy. This is achieved by systematic finitetemperature extension of our recent LKT ground state noninteracting 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 pathintegral Monte Carlo and conventional (orbitaldependent) KohnSham results. The new functional, denoted LKTF, outperforms the previous best semilocal 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 noninteracting freeenergy functionals obtained by extension from ground state orbitalfree kinetic energy functionals.},
doi = {10.1103/PhysRevB.101.075116},
journal = {Physical Review B},
number = 7,
volume = 101,
place = {United States},
year = {2020},
month = {2}
}
Web of Science
Works referenced in this record:
Exact properties of the Pauli potential for the square root of the electron density and the kinetic energy functional
journal, July 1988
 Levy, Mel
 Physical Review A, Vol. 38, Issue 2
Kinetic energy density of nearly free electrons. I. Response functionals of the external potential
journal, September 2019
 Witt, William C.; Carter, Emily A.
 Physical Review B, Vol. 100, Issue 12
Transferable local pseudopotentials for magnesium, aluminum and silicon
journal, January 2008
 Huang, Chen; Carter, Emily A.
 Physical Chemistry Chemical Physics, Vol. 10, Issue 47
Trivial constraints on orbitalfree kinetic energy density functionals
journal, March 2018
 Luo, Kai; Trickey, S. B.
 Chemical Physics Letters, Vol. 695
Semilocal Pauli–Gaussian Kinetic Functionals for OrbitalFree Density Functional Theory Calculations of Solids
journal, July 2018
 Constantin, Lucian A.; Fabiano, Eduardo; Della Sala, Fabio
 The Journal of Physical Chemistry Letters, Vol. 9, Issue 15
Orbitalfree density functional theory correctly models quantum dots when asymptotics, nonlocality, and nonhomogeneity are accounted for
journal, July 2019
 Mi, Wenhui; Pavanello, Michele
 Physical Review B, Vol. 100, Issue 4
Introducing PROFESS 3.0: An advanced program for orbitalfree density functional theory molecular dynamics simulations
journal, May 2015
 Chen, Mohan; Xia, Junchao; Huang, Chen
 Computer Physics Communications, Vol. 190
Upper bound to the gradientbased kinetic energy density of noninteracting electrons in an external potential
journal, August 2019
 Witt, William C.; Jiang, Kaili; Carter, Emily A.
 The Journal of Chemical Physics, Vol. 151, Issue 6
Kinetic energy density of nearly free electrons. II. Response functionals of the electron density
journal, September 2019
 Witt, William C.; Carter, Emily A.
 Physical Review B, Vol. 100, Issue 12
Gradient correction to the statistical electronic free energy at nonzero temperatures: Application to equationofstate calculations
journal, August 1979
 Perrot, F.
 Physical Review A, Vol. 20, Issue 2
On the eigenfunctions of manyparticle systems in quantum mechanics
journal, January 1957
 Kato, Tosio
 Communications on Pure and Applied Mathematics, Vol. 10, Issue 2
Equations of State of Elements Based on the Generalized FermiThomas Theory
journal, May 1949
 Feynman, R. P.; Metropolis, N.; Teller, E.
 Physical Review, Vol. 75, Issue 10
Frontiers and Challenges in Warm Dense Matter
book, January 2014
 Graziani, Frank; Desjarlais, Michael P.; Redmer, Ronald
 Lecture Notes in Computational Science and Engineering, Vol. 96
Approximations for FermiDirac integrals, especially the function used to describe electron density in a semiconductor
journal, November 1982
 Blakemore, J. S.
 SolidState Electronics, Vol. 25, Issue 11
Status of freeenergy representations for the homogeneous electron gas
journal, May 2019
 Karasiev, Valentin V.; Trickey, S. B.; Dufty, James W.
 Physical Review B, Vol. 99, Issue 19
Nonlocal kinetic energy functionals by functional integration
journal, May 2018
 Mi, Wenhui; Genova, Alessandro; Pavanello, Michele
 The Journal of Chemical Physics, Vol. 148, Issue 18
A new method for the electronic structure of metals
journal, March 1964
 Heine, V.; Abarenkov, I.
 Philosophical Magazine, Vol. 9, Issue 99
Extended ThomasFermi theory at finite temperature
journal, November 1985
 Bartel, J.; Brack, M.; Durand, M.
 Nuclear Physics A, Vol. 445, Issue 2
Finitetemperature orbitalfree DFT molecular dynamics: Coupling Profess and Quantum Espresso
journal, December 2014
 Karasiev, Valentin V.; Sjostrom, Travis; Trickey, S. B.
 Computer Physics Communications, Vol. 185, Issue 12
Recent developments in the ABINIT software package
journal, August 2016
 Gonze, X.; Jollet, F.; Abreu Araujo, F.
 Computer Physics Communications, Vol. 205
Inhomogeneous Electron Gas
journal, November 1964
 Hohenberg, P.; Kohn, W.
 Physical Review, Vol. 136, Issue 3B, p. B864B871
A pseudopotential total energy study of impuritypromoted intergranular embrittlement
journal, January 1990
 Goodwin, L.; Needs, R. J.; Heine, V.
 Journal of Physics: Condensed Matter, Vol. 2, Issue 2
Ab initio ExchangeCorrelation Free Energy of the Uniform Electron Gas at Warm Dense Matter Conditions
journal, September 2017
 Groth, Simon; Dornheim, Tobias; Sjostrom, Travis
 Physical Review Letters, Vol. 119, Issue 13
Jelliumwithgap model applied to semilocal kinetic functionals
journal, March 2017
 Constantin, Lucian A.; Fabiano, Eduardo; Śmiga, Szymon
 Physical Review B, Vol. 95, Issue 11
Nonlocal kinetic energy functional from the jelliumwithgap model: Applications to orbitalfree density functional theory
journal, May 2018
 Constantin, Lucian A.; Fabiano, Eduardo; Della Sala, Fabio
 Physical Review B, Vol. 97, Issue 20
Pseudopotentials periodic table: From H to Pu
journal, December 2014
 Dal Corso, Andrea
 Computational Materials Science, Vol. 95
Thermal Properties of the Inhomogeneous Electron Gas
journal, March 1965
 Mermin, N. David
 Physical Review, Vol. 137, Issue 5A
Nonempirical generalized gradient approximation freeenergy functional for orbitalfree simulations
journal, October 2013
 Karasiev, Valentin V.; Chakraborty, Debajit; Shukruto, Olga A.
 Physical Review B, Vol. 88, Issue 16
Firstprinciples equationofstate table of deuterium for inertial confinement fusion applications
journal, December 2011
 Hu, S. X.; Militzer, B.; Goncharov, V. N.
 Physical Review B, Vol. 84, Issue 22
A simple generalized gradient approximation for the noninteracting kinetic energy density functional
journal, July 2018
 Luo, Kai; Karasiev, Valentin V.; Trickey, S. B.
 Physical Review B, Vol. 98, Issue 4
Generalizedgradientapproximation noninteracting freeenergy functionals for orbitalfree density functional calculations
journal, September 2012
 Karasiev, Valentin V.; Sjostrom, Travis; Trickey, S. B.
 Physical Review B, Vol. 86, Issue 11
Accurate Homogeneous Electron Gas ExchangeCorrelation Free Energy for Local SpinDensity Calculations
journal, February 2014
 Karasiev, Valentin V.; Sjostrom, Travis; Dufty, James
 Physical Review Letters, Vol. 112, Issue 7
Semilocal kinetic energy functionals with parameters from neutral atoms
journal, October 2019
 Lehtomäki, Jouko; LopezAcevedo, Olga
 Physical Review B, Vol. 100, Issue 16
Nonempirical Semilocal FreeEnergy Density Functional for Matter under Extreme Conditions
journal, February 2018
 Karasiev, Valentin V.; Dufty, James W.; Trickey, S. B.
 Physical Review Letters, Vol. 120, Issue 7
Efficient Calculation of Electronic Structure Using O(N) Density Functional Theory
journal, August 2017
 Nakata, Ayako; Futamura, Yasunori; Sakurai, Tetsuya
 Journal of Chemical Theory and Computation, Vol. 13, Issue 9
SelfConsistent Equations Including Exchange and Correlation Effects
journal, November 1965
 Kohn, W.; Sham, L. J.
 Physical Review, Vol. 140, Issue 4A, p. A1133A1138
Introducing PROFESS 3.0: An advanced program for orbitalfree density functional theory molecular dynamics simulations
dataset, January 2019
 Chen, Mohan
 Mendeley