The use of the angular median potential as a temperature-independent spherical reference system for approximating molecular fluids is tested for its predictions of thermodynamics. Calculations have been carried out for a wide range of homonuclear diatomics with continuous atom-atom potentials believed to be representative of the full range of simulation data available for such systems. The results for the pressure are surprisingly good both in the detonation regime and around the triple point. In the latter case, however, the internal energies for highly elongated molecules with attractive potential wells are considerably too positive. Comparison with other perturbation theories indicates that the median reference system gives better pressures but poorer energies than RAM, and that in many cases, especially for purely repulsive potentials, it gives results of comparable accuracy to those obtained with nonspherical reference systems.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry