Theory and Monte Carlo simulation of the ideal gas with shell particles in the canonical, isothermal–isobaric, grand canonical, and Gibbs ensembles

Abstract

Theories of small systems play an important role in the fundamental understanding of finite size effects in statistical mechanics, as well as the validation of molecular simulation results as no computer can simulate fluids in the thermodynamic limit. Previously, a shell particle was included in the isothermal–isobaric ensemble in order to resolve an ambiguity in the resulting partition function. The shell particle removed either redundant volume states or redundant translational degrees of freedom of the system and yielded quantitative differences from traditional simulations in this ensemble. In this work, we investigate the effect of including a shell particle in the canonical, grand canonical, and Gibbs ensembles. For systems comprised of a pure component ideal gas, analytical expressions for various thermodynamic properties are obtained. We also derive the Metropolis Monte Carlo simulation acceptance criteria for these ensembles with shell particles, and the results of the simulations of an ideal gas are in excellent agreement with the theoretical predictions. The system size dependence of various important ensemble averages is also analyzed.