Optimal orbitals from energy fluctuations in correlated wave functions

TL;DR

This paper introduces a quantum Monte Carlo method to optimize orbitals in correlated wave functions by minimizing energy fluctuations, applicable to atoms, molecules, and solids.

Contribution

It presents a novel self-consistent scheme for determining optimal orbitals based on energy fluctuation fitting in quantum Monte Carlo calculations.

Findings

Method successfully applied to carbon and neon atoms.

Orbitals optimized for energy stationarity in correlated wave functions.

Feasible for atoms, molecules, and solids.

Abstract

A quantum Monte Carlo method of determining Jastrow-Slater wave functions for which the energy is stationary with respect to variations in the single-particle orbitals is presented. A potential is determined by a least-squares fitting of fluctuations in the energy with a linear combination of one-body operators. This potential is used in a self-consistent scheme for the orbitals whose solution ensures that the energy of the correlated wave function is stationary with respect to variations in the orbitals. The method is feasible for atoms, molecules, and solids and is demonstrated for the carbon and neon atoms.