All-electron quantum Monte Carlo calculations for the noble gas atoms He to Xe

TL;DR

This paper presents all-electron quantum Monte Carlo calculations for noble gas atoms from helium to xenon, analyzing the accuracy, computational cost, and challenges associated with increasing atomic number.

Contribution

It provides a systematic study of all-electron VMC and DMC calculations for noble gases, highlighting the scalability and quality of wave functions across different atoms.

Findings

DMC calculations are feasible for all noble gases studied.

The quality of wave functions decreases with increasing atomic number.

Computational cost scales with atomic number Z.

Abstract

We report all-electron variational and diffusion quantum Monte Carlo (VMC and DMC) calculations for the noble gas atoms He, Ne, Ar, Kr, and Xe. The calculations were performed using Slater-Jastrow wave functions with Hartree-Fock single-particle orbitals. The quality of both the optimized Jastrow factors and the nodal surfaces of the wave functions declines with increasing atomic number Z, but the DMC calculations are tractable and well behaved in all cases. We discuss the scaling of the computational cost of DMC calculations with Z.