Classical statistical mechanics in the μVL and μpR ensembles.

Abstract

Molecular expressions for thermodynamic properties and derivatives of the entropy up to third order in the adiabatic grand-isochoric μVL and adiabatic grand-isobaric μpR ensembles are systematically derived using the methodology developed by Lustig for the microcanonical and canonical ensembles [J. Chem. Phys. 100, 3048 (1994)10.1063/1.466446; Mol. Phys. 110, 3041 (2012)10.1080/00268976.2012.695032]. They are expressed by phase-space functions, which represent derivatives of the entropy with respect to the chemical potential, the volume, and the Hill energy L in the μVL ensemble and with respect to the chemical potential, the pressure, and the Ray energy R in the μpR ensemble. The derived expressions are validated for both ensembles by Monte Carlo simulations for the simple Lennard-Jones model fluid at three selected state points.