An explicit expression for finite-size corrections to the chemical potential

Abstract

In this article an expression is derived for the finite-size corrections to the excess chemical potential in an N-particle system with periodic boundary conditions. The leading N-dependence of the chemical potential is predicted to be proportional to 1/N. The authors derive a simple expression relating the coefficient of this 1/N-term to the compressibility of the system. In order to test the present predictions, Monte Carlo simulations were performed in which the chemical potential of the hard-sphere fluid and of the Lennard-Jones fluid were calculated using the Widom particle insertion method. The results of these simulations are in excellent agreement with the predicted N-dependence.