Predicting virial coefficients and alchemical transformations by extrapolating Mayer-sampling Monte Carlo simulations

Published

December 20, 2017

Author(s)

Harold W. Hatch, Nathan Mahynski, Marco A. Blanco Medina, Vincent K. Shen, Sally Jiao

Abstract

Virial coefficients are predicted over a large range of both temperatures and model parameter values (e.g., alchemical transformation) from an individual Mayer-sampling Monte Carlo simulation by statistical mechanical extrapolation with minimal increase in computational cost. With this extrapolation method, a Mayersampling Monte Carlo simulation of SPC/E water is able to quantitatively predict the second virial coefficient as a continuous function spanning over four orders of magnitude in value and over three orders of magnitude in temperature with less than a 2% deviation. In addition, the same simulation predicts the second virial coefficient if the site charges were scaled by a constant factor, from an increase of 40% all the way to no charge at all. This method is also shown to perform well for the third virial coefficient and the exponential parameter for a Lennard-Jones fluid. Example code is provided at https://github.com/usnistgov/mayer- extrapolation.

Citation

The Journal of Chemical Physics

Volume

147

Pub Type

Journals

Download Paper

https://doi.org/10.1063/1.5016165

Keywords

virial coefficients, Mayer-sampling Monte Carlo, alchemical transformation, temperature

Citation

Hatch, H. , Mahynski, N. , Blanco, M. , Shen, V. and Jiao, S. (2017), Predicting virial coefficients and alchemical transformations by extrapolating Mayer-sampling Monte Carlo simulations, The Journal of Chemical Physics, [online], https://doi.org/10.1063/1.5016165 (Accessed October 7, 2025)