Development of an analytical exponential-6 equation of state through Monte Carlo simulations.

Abstract

The exponential-6 (exp-6) potential is commonly used to model fluids at high densities. In this paper, I propose a new equation of state (EOS) in the form of an analytical expression for the excess Helmholtz free energy of an exp-6 fluid. The EOS is based on extensive Monte Carlo simulations and therefore combines the excellent accuracy of the simulations with the numerical efficiency of a polynomial expression. The mean relative error in compressibility factor and internal energy is 0.14% and 0.25% respectively, which is a significant improvement over statistical mechanical theories. The EOS was implemented into a thermochemical code in order to optimize gas parameters and evaluate its performance on pure gas data, shock compression and detonation properties. Predicted gas densities, heat capacities and speed of sound for pure gases were generally within experimental uncertainties at pressures up to 1GPa and temperatures above 300K. For polar molecules, a simple free energy correction was introduced which greatly improved accuracy at low temperature. Calculated shock Hugoniots showed excellent agreement with experimental values up to 150GPa and 10 000K, and the detonation performance was accurately predicted for a number of different types of explosives.