Scheme for adding electron-nucleus cusps to Gaussian orbitals

TL;DR

This paper introduces a simple method to incorporate correct electron-nucleus cusps into Gaussian orbitals, improving the efficiency and accuracy of quantum Monte Carlo calculations for atoms and molecules.

Contribution

A new scheme for adding electron-nucleus cusps to Gaussian orbitals, enhancing the performance of all-electron VMC and DMC methods.

Findings

Significantly reduces local energy variance in calculations.

Slightly improves variational energies.

Applicable to a wide range of atoms and molecules.

Abstract

A simple scheme is described for introducing the correct cusps at nuclei into orbitals obtained from Gaussian basis set electronic structure calculations. The scheme is tested with all-electron variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods for the Ne atom, the H2 molecule, and 55 molecules from a standard benchmark set. It greatly reduces the variance of the local energy in all cases and slightly improves the variational energy. This scheme yields a general improvement in the efficiency of all-electron VMC and DMC calculations using Gaussian basis sets.