First-principles derivation and properties of density-functional average-atom models

Abstract

Finiteerature Kohn-Sham density functional theory (KS-DFT) is a widely-used method in warm dense matter (WDM) simulations and diagnostics. Unfortunately, full KS-DFT-molecular dynamics models scale unfavourably with temperature and there remains uncertainty regarding the performance of existing approximate exchange-correlation (XC) functionals under WDM conditions. Of particular concern is the expected explicit dependence of the XC functional on temperature, which is absent from most approximations. Average-atom (AA) models, which significantly reduce the computational cost of KS-DFT calculations, have therefore become an integral part of WDM modeling. In this paper, we present a derivation of a first-principles AA model from the fully-interacting many-body Hamiltonian, carefully analyzing the assumptions made and terms neglected in this reduction. We explore the impact of different choices within this model - such as boundary conditions and XC functionals - on common properties in WDM, for example equation-of-state data, ionization degree and the behavior of the frontier energy levels. Furthermore, drawing upon insights from ground-state KS-DFT, we discuss the likely sources of error in KS-AA models and possible strategies for mitigating such errors.