The calculation of chemical potential of organic solutes in dense liquid phases by using expanded ensemble Monte Carlo simulations

Abstract

In this work, the chemical potentials of organic compounds in dense liquid phases are calculated by using expanded ensemble Monte Carlo simulations. To make insertion of a solute molecule efficiently, Lennard-Jones size parameters and bond lengths are varied with coupling parameter. A robust adaptive scheme is proposed in order to determine biasing weights during the simulation, which enhances the efficiency and applicability of the expanded ensemble method. Using the proposed simulation technique, chemical potentials of organic molecules in dense liquid phases are obtained from a single run of simulation. The excess chemical potentials of several hydrocarbon molecules including n-alkanes, benzene, toluene, and ethanol in aqueous phases at infinite dilution as well as in their pure liquid phases are calculated at 298 K and 1 atm, and simulation results are compared with experimental data.