State conditions transferability of vapor–liquid equilibria via fluctuation solution theory with correlation function integrals from molecular dynamics simulation

Christensen, Steen; Peters, Günther H.J.; Hansen, Flemming Yssing; O’Connell, John P.; Abildskov, Jens

doi:10.1016/j.fluid.2007.06.026

Cited by 20 publications

(19 citation statements)

References 14 publications

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“…29,[37][38][39][40][41][42][43] Under isothermal conditions, the second derivatives in the GCE only involve the particle number fluctuations between all possible pairs of species. These fluctuations are then related to second derivatives of the Gibbs free energy for an equivalent closed system.…”

Section: Theorymentioning

confidence: 99%

Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

Ploetz

Smith

2015

The Journal of Chemical Physics

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Kirkwood-Buff or Fluctuation Solution Theory can be used to provide experimental pair fluctuations, and/or integrals over the pair distribution functions, from experimental thermodynamic data on liquid mixtures. Here, this type of approach is used to provide triplet and quadruplet fluctuations, and the corresponding integrals over the triplet and quadruplet distribution functions, in a purely thermodynamic manner that avoids the use of structure factors. The approach is then applied to binary mixtures of water + methanol and benzene + methanol over the full composition range under ambient conditions. The observed correlations between the different species vary significantly with composition. The magnitude of the fluctuations and integrals appears to increase as the number of the most polar molecule involved in the fluctuation or integral also increases. A simple physical picture of the fluctuations is provided to help rationalize some of these variations. C 2015 AIP Publishing LLC. [http://dx

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Section: Theorymentioning

confidence: 99%

Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

Ploetz

Smith

2015

The Journal of Chemical Physics

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“…Matteoli and Mansoori (Matteoli and Mansoori 1995) (Christensen et al 2007a;Christensen et al 2007b;Christensen et al 2007c) addressed molecular simulations of systems resembling real molecules.…”

Section: Long Range Modelingmentioning

confidence: 99%

“…Note that this approach has only been successfully tested on pure fluids. The main limitation of both methods (Christensen et al 2007a;Christensen et al 2007b;Christensen et al 2007c;Wedberg, Peters, and Abildskov 2008) is that they apply only to systems where the TCF tails can be approximated by the model equations, which may not be true in general.…”

Section: Long Range Modelingmentioning

confidence: 99%

- Global and Local Properties of Mixtures: An Expanded Paradigm for the Study of Mixtures

2016

Fluctuation Theory of Solutions

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“…4 The integrals have been extensively used in the development of accurate force fields for fluid mixtures. [5][6][7][8][9][10][11][12] Christensen et al 4,13,14 utilized the integrals in a methodology for predicting the excess Gibbs energy of liquid mixtures. They simulated the mixture at a few compositions using molecular dynamics and then regressed parameters of the modified Margules G E model.…”

Section: Introductionmentioning

confidence: 99%

“…For substances exhibiting nearly ideal behavior in the vapor phase, this approach has proven to be a viable alternative for predicting vapor-liquid equilibria. 13,14 In addition, correlation function integrals themselves are interesting properties as several established corresponding state theories for thermodynamic properties are based on modeling direct correlation function integrals. 23-29 a) Author to whom correspondence should be addressed.…”

Section: Introductionmentioning

confidence: 99%

Pair correlation function integrals: Computation and use

Wedberg

O’Connell

Peters

et al. 2011

The Journal of Chemical Physics

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We describe a method for extending radial distribution functions obtained from molecular simulations of pure and mixed molecular fluids to arbitrary distances. The method allows total correlation function integrals to be reliably calculated from simulations of relatively small systems. The long-distance behavior of radial distribution functions is determined by requiring that the corresponding direct correlation functions follow certain approximations at long distances. We have briefly described the method and tested its performance in previous communications [R. Wedberg, J. P. O'Connell, G. H. Peters, and J. Abildskov, Mol. Simul. 36, 1243 (2010); Fluid Phase Equilib. 302, 32 (2011)], but describe here its theoretical basis more thoroughly and derive long-distance approximations for the direct correlation functions. We describe the numerical implementation of the method in detail, and report numerical tests complementing previous results. Pure molecular fluids are here studied in the isothermal-isobaric ensemble with isothermal compressibilities evaluated from the total correlation function integrals and compared with values derived from volume fluctuations. For systems where the radial distribution function has structure beyond the sampling limit imposed by the system size, the integration is more reliable, and usually more accurate, than simple integral truncation.

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State conditions transferability of vapor–liquid equilibria via fluctuation solution theory with correlation function integrals from molecular dynamics simulation

Cited by 20 publications

References 14 publications

Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

Experimental triplet and quadruplet fluctuation densities and spatial distribution function integrals for liquid mixtures

- Global and Local Properties of Mixtures: An Expanded Paradigm for the Study of Mixtures

Pair correlation function integrals: Computation and use

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