Thermodynamic properties of solutions based on correlation functions

O’Connell, John P.

doi:10.1080/00268977100100031

Cited by 148 publications

(82 citation statements)

References 11 publications

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“…In the case of electrolytes the KB integrals are related to the individual ion integrals through a series of electroneutrality conditions. For the cosolvent we have, 21,28 (27) and, (28) In addition, for the salt distribution around the solute one can write, (29) which combined with the electroneutrality constraint equation, (30) provides, (31) Ben-Naim has pointed out that the above expressions for salts are not due to the ionic nature of the interactions per se, but the fact that the cation and anion concentrations cannot be varied independently. 18 Hence, combining Equation 22, Equation 27, and Equation 31 provides, (32) which holds for any solvent and cosolvent concentration, and where we have focused on the cation as the single independent species.…”

Section: Electrolyte Cosolventsmentioning

confidence: 99%

On the Theory of Solute Solubility in Mixed Solvents

Smith

Mazo

2008

J. Phys. Chem. B

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A series of equations are developed for the study of the effects of cosolvents on the solubility of a solute in mixed solutions where the solute displays a finite solubility. The equations differ depending on the scale used for the solute (and cosolvent) concentrations. The expressions use Kirkwood-Buff integrals to relate the changes in solubility to changes in the local solution composition around the solute, and can be applied to study any type of ternary system including electrolyte cosolvents. The expressions provided here differ from previous approaches due to the use of a semi open ensemble, and the extension to finite solute solubilities.

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Section: Electrolyte Cosolventsmentioning

confidence: 99%

On the Theory of Solute Solubility in Mixed Solvents

Smith

Mazo

2008

J. Phys. Chem. B

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“…(1), (2), and (4) the direct correlation function can be written as a sum of isotropic and anisotropic parts,…”

Section: Molecular Correlation Functionsmentioning

confidence: 99%

“…Integrals of the total correlation function provide a direct link between the microscopic structure of a fluid mixture and macroscopic thermodynamic derivative properties by a set of algebraic relations termed fluctuation solution theory, [1][2][3] or Kirkwood-Buff theory. Isothermal compressibilities, partial molar volumes, and composition derivatives of activity coefficients are expressed in terms of these integrals.…”

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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“…After some time, the basic formulation for activities and compressibilities was redone for the whole range of concentrations and for expressions that avoided matrix complexities by involving integrals of direct correlation functions (O'Connell 1971b). It was noted much later that for molecular systems, these relations depended on the applicability of the "weak approximation" for angle-dependent intermolecular forces (Gray and Gubbins 1984;O'Connell 1994).…”

Section: Introductionmentioning

confidence: 99%

- Accurate Force Fields for Molecular Simulation

2016

Fluctuation Theory of Solutions

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Thermodynamic properties of solutions based on correlation functions

Cited by 148 publications

References 11 publications

On the Theory of Solute Solubility in Mixed Solvents

On the Theory of Solute Solubility in Mixed Solvents

Pair correlation function integrals: Computation and use

- Accurate Force Fields for Molecular Simulation

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