Microcanonical Monte Carlo simulation of thermodynamic properties

Abstract

A rigorous sampling procedure in configurational phase space is used to simulate any thermodynamic property in the microcanonical ensemble. It is shown how two classical choices of W in Boltzmann’s S=kB ln W differ for small systems and become numerically equivalent in the thermodynamic limit. The same holds true for the comparison with classical molecular dynamics simulations. A comparison with the best empirical equations of state for the Lennard-Jones system shows that this Monte Carlo method is as accurate and reliable as any other simulation technique.