Computational methods in Coupled Electron-Ion Monte Carlo

TL;DR

This paper introduces an improved sampling algorithm for the Coupled Electron-Ion Monte Carlo method, enhancing efficiency in simulating high-pressure metallic hydrogen by leveraging Reptation Quantum Monte Carlo and variational energy estimates.

Contribution

The paper presents a novel sampling algorithm within RQMC for CEIMC, improving efficiency and accuracy in electronic and proton sampling for metallic hydrogen.

Findings

Enhanced sampling efficiency with the new algorithm

Accurate electronic energy estimates via variational methods

Successful application to high-pressure metallic hydrogen

Abstract

In the last few years we have been developing a Monte Carlo simulation method to cope with systems of many electrons and ions in the Born-Oppenheimer (BO) approximation, the Coupled Electron-Ion Monte Carlo Method (CEIMC). Electronic properties in CEIMC are computed by Quantum Monte Carlo (QMC) rather than by Density Functional Theory (DFT) based techniques. CEIMC can, in principle, overcome some of the limitations of the present DFT based ab initio dynamical methods. Application of the new method to high pressure metallic hydrogen has recently appeared. In this paper we present a new sampling algorithm that we have developed in the framework of the Reptation Quantum Monte Carlo (RQMC) method chosen to sample the electronic degrees of freedom, thereby improving its efficiency. Moreover, we show here that, at least for the case of metallic hydrogen, variational estimates of the electronic energies lead to an accurate sampling of the proton degrees of freedom.