Comparison of Density Functional Approximations and the Finite-temperature Hartree-Fock Approximation in Warm Dense Lithium

TL;DR

This paper compares finite-temperature Hartree-Fock and density functional theory approaches in warm dense lithium, highlighting qualitative differences and assessing pseudopotential reliability for high-density simulations.

Contribution

It provides a detailed comparison of exchange-only models and develops reliable all-electron PAW datasets for high-density lithium simulations.

Findings

Significant qualitative differences between models in warm dense conditions.

Identification of density ranges where pseudopotentials are reliable.

Development of all-electron PAW datasets valid up to 80 g/cm$^3$.

Abstract

We compare the behavior of the finite-temperature Hartree-Fock model with that of thermal density functional theory using both ground-state and temperature-dependent approximate exchange functionals. The test system is bcc Li in the temperature-density regime of warm dense matter (WDM). In this exchange-only case, there are significant qualitative differences in results from the three approaches. Those differences may be important for Born-Oppenheimer molecular dynamics studies of WDM with ground-state approximate density functionals and thermal occupancies. Such calculations require reliable regularized potentials over a demanding range of temperatures and densities. By comparison of pseudopotential and all-electron results at ${\mathrm T} = 0$K for small Li clusters of local bcc symmetry and bond-lengths equivalent to high density bulk Li, we determine the density ranges for which standard projector augmented wave (PAW) and norm-conserving pseudopotentials are reliable. Then we construct and use all-electron PAW data sets with a small cutoff radius which are valid for lithium densities up to at least 80 g/cm$^3$.