Framework for solvation in quantum Monte Carlo

TL;DR

This paper presents a new quantum Monte Carlo framework that models solvation using classical density-functional theory, enabling efficient calculation of free energies without explicit solvent electrons or thermodynamic sampling.

Contribution

It introduces a rigorous, computationally efficient method for solvation in quantum Monte Carlo that simplifies calculations and broadens applicability to condensed matter challenges.

Findings

Promising results with small convergence errors for test molecules

Applicable to studying transition states in liquid environments

No need for explicit solvent electrons or thermodynamic sampling

Abstract

Employing a classical density-functional description of liquid environments, we introduce a rigorous method for the diffusion quantum Monte Carlo calculation of free energies and thermodynamic averages of solvated systems that requires neither thermodynamic sampling nor explicit solvent electrons. We find that this method yields promising results and small convergence errors for a set of test molecules. It is implemented readily and is applicable to a range of challenges in condensed matter, including the study of transition states of molecular and surface reactions in liquid environments.