Smooth relativistic Hartree-Fock pseudopotentials for H to Ba and Lu to Hg

TL;DR

This paper introduces smooth relativistic Hartree-Fock pseudopotentials and spin-orbit operators for a wide range of elements, improving their physical behavior and compatibility with quantum chemistry calculations.

Contribution

The authors develop and present analytically representable relativistic pseudopotentials for elements H to Ba and Lu to Hg, removing unphysical behaviors.

Findings

Pseudopotentials are smooth and physically accurate.

Suitable for Hartree-Fock and correlated wave function methods.

Applicable in diffusion quantum Monte Carlo calculations.

Abstract

We report smooth relativistic Hartree-Fock pseudopotentials (also known as averaged relativistic effective potentials or AREPs) and spin-orbit operators for the atoms H to Ba and Lu to Hg. We remove the unphysical extremely non-local behaviour resulting from the exchange interaction in a controlled manner, and represent the resulting pseudopotentials in an analytic form suitable for use within standard quantum chemistry codes. These pseudopotentials are suitable for use within Hartree-Fock and correlated wave function methods, including diffusion quantum Monte Carlo calculations.