A perturbation theory for solvation thermodynamics: Dipolar-quadrupolar liquids

Dmitry Matyushov, Gregory A. Voth

Research output: Contribution to journalArticle

61 Citations (Scopus)

Abstract

The thermodynamics of solvation of a dipole in hard sphere solvents with dipoles and quadrupoles is studied by using the Padé approximation for the perturbation expansion of the solvation chemical potential and compared to Monte Carlo simulations. Solvation chemical potentials, energies, and entropies of solvation are obtained at different dipolar and quadrupolar solvent strengths. The effect of nonlinear solvation is analyzed and found not to exceed 10% in the parameter range studied. An agreement between the simulations and the analytical theory is obtained by an empirical rescaling of the triple perturbation integrals of the perturbation expansion. This rescaling does not, however, provide a quantitatively correct partitioning of the solvation free energy into the energy and entropy of solvation.

Original languageEnglish (US)
Pages (from-to)3630-3638
Number of pages9
JournalJournal of Chemical Physics
Volume111
Issue number8
StatePublished - Aug 22 1999
Externally publishedYes

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Solvation
solvation
perturbation theory
Thermodynamics
thermodynamics
Liquids
liquids
Chemical potential
perturbation
Entropy
entropy
dipoles
expansion
Potential energy
Free energy
simulation
quadrupoles
potential energy
free energy
approximation

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

A perturbation theory for solvation thermodynamics : Dipolar-quadrupolar liquids. / Matyushov, Dmitry; Voth, Gregory A.

In: Journal of Chemical Physics, Vol. 111, No. 8, 22.08.1999, p. 3630-3638.

Research output: Contribution to journalArticle

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