A computer simulation method for the calculation of equilibrium constants for the formation of physical clusters of molecules: Application to small water clusters

TLDR: In this article, a molecular dynamics computer simulation method for calculating equilibrium constants for the formation of physical clusters of molecules is presented, which is based on Hill's formal theory of physical clustering.

Abstract: We present a molecular dynamics computer simulation method for calculating equilibrium constants for the formation of physical clusters of molecules. The method is based on Hill’s formal theory of physical clusters. In the method, a molecular dynamics calculation is used to calculate the average potential energy of a cluster of molecules as a function of temperature, and the equilibrium constants are calculated from the integral of the energy with respect to reciprocal temperature. The method is illustrated by calculations of the equilibrium constants for the formation of clusters of two to five water molecules that interact with each other by an intermolecular potential devised by Watts. The method is compared with other procedures for calculating the thermodynamic properties of clusters.