J Chem Phys. 2018 Dec 21;149(23):234907. doi: 10.1063/1.5047448.

A semianalytical "reverse" approach to link structure and microscopic interactions in two-Yukawa competing fluids.

The Journal of chemical physics

Jean-Louis Bretonnet, Jean-Marc Bomont, Dino Costa

PMID: 30579317 DOI: 10.1063/1.5047448

Abstract

We study theoretically a prototype hard-sphere two-Yukawa model with competing interactions, under thermodynamic conditions associated with the formation of clusters. We adopt the analytically solvable random phase approximation and show that this theory predicts reasonably well the structure of the fluid-in comparison with exact Monte Carlo results-within a unique parameterization of the direct correlation function inside the hard core of particles. In particular, the theory follows correctly the development, in the structure factor, of a local peak at low wavevectors, as peculiarly associated with the onset of aggregation. We then model the direct correlation function in the same wavevector regime by a Gaussian function, so as to systematically investigate, in a "reverse" scheme, how varying the properties of the local peak modifies the original underlying competing interaction. We show that large variations in the height of the peak are generally associated with comparatively smaller variations in the height of the microscopic repulsive barrier; moreover, the shrinking and shifting towards lower wavevectors of the peak may be interpreted in terms of the displacement of the barrier, producing a substantial enlargement of the range of both the attractive and repulsive contributions to the interaction potential. Finally, we document the way the repulsive barrier tends to vanish as the two-Yukawa fluid approaches a "simple fluid" behavior, heralding the onset of a liquid-vapor phase separation.

Publication Types

• Journal Article