Microcanonical ensemble simulation method applied to discrete potential fluids

Abstract

In this work we extend the applicability of the microcanonical ensemble simulation method, originally proposed to study the Ising model (A. Hüller and M. Pleimling, Int. Journal of Modern Physics C, 13, 947 (2002), arxiv:cond-mat/0110090), to the case of simple fluids. An algorithm is developed by measuring the transition rates probabilities between macroscopic states, that has as advantage with respect to conventional Monte Carlo NVT (MC-NVT) simulations that a continuous range of temperatures are covered in a single run. For a given density, this new algorithm provides the inverse temperature, that can be parametrized as a function of the internal energy, and the isochoric heat capacity is then evaluated through a numerical derivative. As an illustrative example we consider a fluid composed of particles interacting via a square-well (SW) pair potential of variable range. Equilibrium internal energies and isochoric heat capacities are obtained with very high accuracy compared with data obtained from MC-NVT simulations. These results are important in the context of the application of Hüller-Pleimling method to discrete-potential systems, that are based on a generalization of the SW and Square-Shoulder fluids properties.