Thermodynamic scaling Gibbs ensemble Monte Carlo: a new method for determination of phase coexistence properties of fluids

摘要

Valleau's thermodynamic scaling Monte Carlo concept is combined with the Gibbs ensemble method for phase coexistence calculations, and phase coexistence properties of several Hamiltonians (potential models) at many temperatures are obtained in a single simulation. The theoretical formulation of the method is presented in detail. An application to the (n — 6) Lennard-Jones family of potentials is demonstrated. The combined method is found to be more efficient than the conventional Gibbs ensemble method when properties of related potential models at many thermodynamic states are of interest. Possible extensions of the combined methodology to mixtures, intermolecular potential model development, and multisegment systems that require configurational-bias sampling are discussed.