Journal of Chemical Physics, Vol.115, No.17, 8231-8237, 2001
Calculation of the chemical potential of chain molecules using the staged particle deletion scheme
A formulation is presented for the calculation of the chemical potential of chain molecules from molecular simulation based on the staged deletion of a test molecule. This formulation is an extension of a formulation presented recently [Boulougouris , Mol. Phys. 96, 905 (1999)] for the case of spherical molecules. An analytical method for the calculation of the volume accessible to a hard-sphere chain molecule is used together with the excluded volume map sampling technique. The new method is applied to a fluid of tangent sphere dimers and to ethane under various conditions. NPT, NVT, and Gibbs ensemble Monte Carlo simulation results are presented. Extensive comparison is made against calculations with the Widom test particle insertion method. In all cases, the new method results in considerable savings in CPU time.