Thermodynamically self-consistent liquid state theories for systems with bounded potentials

Abstract

The mean spherical approximation (MSA) can be solved semi-analytically for the Gaussian core model (GCM) and yields - rather surprisingly - exactly the same expressions for the energy and the virial equations. Taking advantage of this semi-analytical framework, we apply the concept of the self-consistent Ornstein-Zernike approximation (SCOZA) to the GCM: a state-dependent function K is introduced in the MSA closure relation which is determined to enforce thermodynamic consistency between the compressibility route and either the virial or energy route. Utilizing standard thermodynamic relations this leads to two different differential equations for the function K that have to be solved numerically. Generalizing our concept we propose an integro-differential-equation based formulation of the SCOZA which, although requiring a fully numerical solution, has the advantage that it is no longer restricted to the availability of an analytic solution for a particular system. Rather it can be used for an arbitrary potential and even in combination with other closure relations, such as a modification of the hypernetted chain approximation.

11 pages, 11 figures, submitted to J. Chem. Phys

References in corpus (2)

• The Hierarchical Reference Theory as applied to square well fluids of variable range
• Implementation of the Hierarchical Reference Theory for simple one-component fluids

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• Thermodynamic consistency of energy and virial routes: An exact proof within the linearized Debye-Hückel theory
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• Simple relationship between the virial-route hypernetted-chain and the compressibility-route Percus--Yevick values of the fourth virial coefficient