Monte Carlo methods: Application to hydrogen gas and hard spheres

TL;DR

This paper explores advanced Monte Carlo techniques, including quantum and classical methods, to accurately simulate properties of hydrogen gas and hard spheres, introducing new algorithms for optimizing wave functions and reducing computational noise.

Contribution

It introduces the Coupled Electronic-Ionic Monte Carlo (CEIMC) method and new optimization techniques for wave functions, expanding the scope of Monte Carlo simulations for quantum and classical systems.

Findings

CEIMC successfully applied to molecular hydrogen at high temperatures and densities.

New algorithms improve wave function optimization in Variational Monte Carlo.

Enhanced methods reduce noise in quantum Monte Carlo energy calculations.

Abstract

Quantum Monte Carlo (QMC) methods can very accurately compute ground state properties of quantum systems. We applied these methods to a system of boson hard spheres to get exact, infinite system size results for the ground state at several densities. Variational Monte Carlo (VMC) requires optimizing a parameterized wave function to find the minimum energy. We examine several techniques for optimizing VMC wave functions, focusing on the ability to optimize parameters appearing in the Slater determinant. The kinds of problems that can be simulated with Monte Carlo methods are expanded through the development of new algorithms for combining a QMC simulation of the electrons with a classical Monte Carlo simulation for the nuclei, which we call Coupled Electronic-Ionic Monte Carlo (CEIMC). The new CEIMC method is applied to a system of molecular hydrogen at temperatures ranging from 2800K to 4500K and densities from 0.25 to 0.46 g/cm**3. The challenges in constructing an efficient CEIMC simulation center mostly around the noisy results generated from the QMC computations of the electronic energy. The penalty method is a modification of the Metropolis method that can tolerate noise. An improved correlated sampling method, the two-sided energy difference method, is also presented as a method for reducing the noise.