Free Energy Calculations for Lennard-Jones Systems and Water Using the Expanded Ensemble Method. A Monte Carlo and Molecular Dynamics Simulation Study.

Molecular Physics, v.82, pp.455-471 (1994)

A.P.Lyubartsev and Aatto Laaksonen,

Div.of Physical Chemistry, Arrhenius Laboratory, University of Stockholm, S-10691, Stockholm, SWEDEN

Pavel N.Vorontsov-Velyaminov,

Physics Faculty, St.Petersburg State University, 198904, St.Petersburg, RUSSIA

Abstract.

The method of expanded ensembles for calculation of free energy in Monte Carlo simulations (Lyubartsev et.al, J.Chem.Phys.,96,1776,1992) is incorporated into molecular dynamics simulations. Calculations of the free energy for the Lennard-Jones system are carried out using both variants of the expanded ensemble method (i.e. Monte Carlo and molecular dynamics simulations) and are shown to give identical results. The free energy for two variants of the simple point charge (SPC) water model (rigid and flexible) is calculated using the Lennard-Jones system as a reference. Numerically very accurate results for the free energy are obtained. The results are in accordance with results obtained using other methods for calculation of free energy in computer simulat ions. The advantages of the presented method and possible applications for calculation of free energies for more complicated molecular systems are discussed.

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