Self-consistent Ornstein-Zernike approximation for molecules with soft cores

TL;DR

This paper extends the Self-Consistent Ornstein-Zernike Approximation (SCOZA) to molecules with soft cores by introducing a temperature-dependent effective hard core, improving the theory's accuracy for real molecular interactions.

Contribution

It incorporates soft core repulsion into SCOZA using a temperature-dependent effective hard core diameter, enhancing the model's realism for molecular liquids.

Findings

The effective hard core diameter depends only on temperature.

Including the repulsive energy contribution improves thermodynamic consistency.

The reformulated SCOZA accurately captures soft core effects.

Abstract

The Self-Consistent Ornstein-Zernike Approximation (SCOZA) is an accurate liquid state theory. So far it has been tied to interactions composed of hard core repulsion and long-range attraction, whereas real molecules have soft core repulsion at short distances. In the present work, this is taken into account through the introduction of an effective hard core with a diameter that depends upon temperature only. It is found that the contribution to the configurational internal energy due to the repulsive reference fluid is of prime importance and must be included in the thermodynamic self-consistency requirement on which SCOZA is based. An approximate but accurate evaluation of this contribution relies on the virial theorem to gauge the amplitude of the pair distribution function close to the molecular surface. Finally, the SCOZA equation is transformed by which the problem is reformulated in terms of the usual SCOZA with fixed hard core reference system and temperature-dependent interaction.