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

J. S. Høye, A. Reiner
2006 Journal of Chemical Physics  
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
more » ... nergy 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.
doi:10.1063/1.2347704 pmid:16999537 fatcat:ld6sybpmu5ha5er3o2clkdcoma