Integral equation theory description of phase equilibria in classical fluids

International audienceWe investigate the temperature threshold whereupon two-Yukawa fluids with microscopic competing interactions transform from normal to cluster fluids. Specifically, we apply two refined, thermodynamically self-consistent integral equation theories of the liquid state to study a family of two-Yukawa models having the same interaction strength, independently on the choice of potential parameters. We find, over the range of potential parameters and fluid densities investigated, an almost linear scaling between the temperature threshold for the cluster formation and the height of repulsive interactions, with higher barriers stabilizing the cluster fluid at higher temperatures. Cluster-cluster correlation lengths seem instead influenced by the long-range features of interactions

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“…(9) given by the PY expression for the hardsphere fluid bridge function at the same density [42,43] -is also reported in…”

Section: Replymentioning

confidence: 75%

Theoretical description of cluster formation in two-Yukawa competing fluids

Costa

Caccamo

Bomont³

et al. 2011

Molecular Physics

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“…It is meanwhile well-known and widely documented that conventional integral equation theories -such as the Percus-Yevick (PY), the hypernetted chain (HNC), or the mean spherical (MSA) approximation -are thermodynamically inconsistent, which means that the various thermodynamic routes to calculate the dimensionless equation of state lead to significantly different results 1,2 . Over the past decades considerable effort has been devoted to the formulation of thermodynamically selfconsistent liquid state theories, which, in turn, have led to an improved description of the structural and thermodynamic properties of liquids with harshly repulsive potentials.…”

Section: Introductionmentioning

confidence: 99%

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

Mladek

Kahl

Neumann

2006

The Journal of Chemical Physics

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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.

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“…The subject of integral equation theory is one of the richest and broadest branches of statistical mechanics. Detailed reviews on this issue may be found in the literature (BARKER; HENDERSON, 1976;CACCAMO, 1996). Therefore, we shall give only a simple preamble to this topic, including solely the theories from which the structure factors have been used to interpret scattering intensities of proteins into aqueous solutions.…”

Section: Prolegomena To Integral Equation Theorymentioning

confidence: 99%

“…However, this equation can only be solved by using approximations known as closure relations. A review on this subject can be found in Caccamo (CACCAMO, 1996). One of these closure relations, which results in analytical solutions for simple interparticle potentials, was formulated by Percus and Yevick (PERCUS;YEVICK, 1958).…”

Section: Monte Carlo Algorithmmentioning

confidence: 99%

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Study on the thermodynamics of bovine serum albumin aqueous solutions: experiments, modeling and molecular simulations.

Franco¹

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Integral equation theory description of phase equilibria in classical fluids

Cited by 256 publications

References 526 publications

Theoretical description of cluster formation in two-Yukawa competing fluids

Theoretical description of cluster formation in two-Yukawa competing fluids

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

Study on the thermodynamics of bovine serum albumin aqueous solutions: experiments, modeling and molecular simulations.

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