Free energy of solvation of a small Lennard–Jones particle

Abstract

Abstract In molecular dynamics (MD) and Monte Carlo (MC) free energy calculations, the choices of the thermodynamic paths from state a to state b affect the accuracy of the result and the efficiency of the programs. Most of the problems occur at the initial stages of growing in a new particle into a solvent. Based on statistical mechanical perturbation theory, an accurate and efficient direct calculation of inserting a small Lennard–Jones particle into solvent is derived. This eliminates the need for calculation of the initial stages of growing in a new particle by MD or MC simulation. Examples are given to show the utility of direct calculation. The recommended procedure is to use direct calculation for a small Lennard–Jones particle and then use MD or MC simulations to calculate the Δ G of changing the small Lennard–Jones particle into the target molecule. © 1994 by John Wiley & Sons, Inc.