Multiple Free Energy Calculations from Single State Point Continuous Fractional Component Monte Carlo Simulation Using Umbrella Sampling

Ahmadreza Rahbari, Remco Hens, Othonas A. Moultos, David Dubbeldam, Thijs J.H. Vlugt*

*Corresponding author for this work

Research output: Contribution to journalArticleScientificpeer-review

5 Citations (Scopus)
42 Downloads (Pure)

Abstract

We introduce an alternative method to perform free energy calculations for mixtures at multiple temperatures and pressures from a single simulation, by combining umbrella sampling and the continuous fractional component Monte Carlo method. One can perform a simulation of a mixture at a certain pressure and temperature and accurately compute the chemical potential at other pressures and temperatures close to the simulation conditions. This method has the following advantages: (1) Accurate estimates of the chemical potential as a function of pressure and temperature are obtained from a single state simulation without additional postprocessing. This can potentially reduce the number of simulations of a system for free energy calculations for a specific temperature and/or pressure range. (2) Partial molar volumes and enthalpies are obtained directly from the estimated chemical potentials. We tested our method for a Lennard-Jones system, aqueous mixtures of methanol at T = 298 K and P = 1 bar, and a mixture of ammonia, nitrogen, and hydrogen at T = 573 K and P = 800 bar. For pure methanol (N = 410 molecules), we observed that the estimated chemical potentials from umbrella sampling are in excellent agreement with the reference values obtained from independent simulations, for ΔT = ±15 K and ΔP = 100 bar (with respect to the simulated system). For larger systems, this range becomes smaller because the relative fluctuations of energy and volume become smaller. Without sufficient overlap, the performance of the method will become poor especially for nonlinear variations of the chemical potential.

Original languageEnglish
Pages (from-to)1757-1767
JournalJournal of chemical theory and computation
Volume16
Issue number3
DOIs
Publication statusPublished - 2020

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