Simple quantitative tests to validate sampling from thermodynamic ensembles

TL;DR

This paper introduces simple statistical tests to verify if molecular simulation algorithms correctly sample the intended thermodynamic ensembles, aiding validation of simulation accuracy across various conditions.

Contribution

It presents accessible statistical procedures for validating thermodynamic ensemble sampling in molecular simulations, including implementation details for end users.

Findings

Tests effectively distinguish proper ensemble sampling

Applicable to constant volume and pressure simulations

Demonstrated utility on model systems

Abstract

It is often difficult to quantitatively determine if a new molecular simulation algorithm or software properly implements sampling of the desired thermodynamic ensemble. We present some simple statistical analysis procedures to allow sensitive determination of whether a de- sired thermodynamic ensemble is properly sampled. We demonstrate the utility of these tests for model systems and for molecular dynamics simulations in a range of situations, includ- ing constant volume and constant pressure simulations, and describe an implementation of the tests designed for end users.