Electronic correlation in nearly free electron metals with beyond-DFT methods

TL;DR

This study compares various beyond-DFT methods to standard DFT in predicting electronic bandwidths of nearly free electron metals, finding local correlations best match experimental ARPES data.

Contribution

It systematically evaluates the effectiveness of multiple beyond-DFT approaches in accurately modeling the electronic structure of simple metals.

Findings

Hybrid functionals increase bandwidths compared to LDA.

G0W0 bands are slightly narrower than LDA.

LDA+eDMFT provides the best agreement with ARPES.

Abstract

For more than three decades, nearly free electron elemental metals have been a topic of debate because the computed bandwidths are significantly wider in the local density approximation to density-functional theory (DFT) than indicated by angle-resolved photoemission (ARPES) experiments. Here, we systematically investigate this using first-principles calculations for alkali and alkaline-earth metals using DFT and various beyond-DFT methods such as meta-GGA, G$_0$W$_0$, hybrid functionals (YS-PBE0, B3LYP), and LDA+eDMFT. We find that the static non-local exchange, as partly included in the hybrid functionals, significantly increase the bandwidths even compared to LDA, while the G$_0$W$_0$ bands are only slightly narrower than in LDA. The agreement with the ARPES is best when the local approximation to the self-energy is used in the LDA+eDMFT method. We infer that even moderately correlated systems with partially occupied s-orbitals, which were assumed to approximate the uniform electron gas, are very well described in terms of short-range dynamical correlations that are only local to an atom.