Generation of thermodynamic data for organic liquid mixtures from molecular simulations

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

“…Fluctuation solution theory (FST) connects microscopic density fluctuations to macroscopic fluid properties [1][2][3]. The key quantity is the static total correlation function integral (TCFI), H ij :…”

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

“…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.…”

“…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.…”

Pair correlation function integrals: Computation and use

“…Perera and Sokolić, 32 and Hess and van der Vegt 33 corrected the sampled distribution functions by rescaling them such that they converged to unity within the sampling limit. Matteoli and Mansoori, 34 Christensen et al, 4 and Wedberg, Peters, and Abildskov 35 fitted the functions to parametric expressions selected by empirical means, which then were used for extrapolation to long range. Another approach proposed by Nichols, Moore, and Wheeler 36 extrapolates the structure factors to zero with polynomials of varying degrees, in order to obtain the correlation function integrals.…”

“…Isothermal compressibilities, partial molar volumes, and composition derivatives of activity coefficients are expressed in terms of these integrals. 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.…”