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Issue 13, 2015
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Determination of partial molar volumes from free energy perturbation theory

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Abstract

Partial molar volume is an important thermodynamic property that gives insights into molecular size and intermolecular interactions in solution. Theoretical frameworks for determining the partial molar volume (V°) of a solvated molecule generally apply Scaled Particle Theory or Kirkwood–Buff theory. With the current abilities to perform long molecular dynamics and Monte Carlo simulations, more direct methods are gaining popularity, such as computing V° directly as the difference in computed volume from two simulations, one with a solute present and another without. Thermodynamically, V° can also be determined as the pressure derivative of the free energy of solvation in the limit of infinite dilution. Both approaches are considered herein with the use of free energy perturbation (FEP) calculations to compute the necessary free energies of solvation at elevated pressures. Absolute and relative partial molar volumes are computed for benzene and benzene derivatives using the OPLS-AA force field. The mean unsigned error for all molecules is 2.8 cm3 mol−1. The present methodology should find use in many contexts such as the development and testing of force fields for use in computer simulations of organic and biomolecular systems, as a complement to related experimental studies, and to develop a deeper understanding of solute–solvent interactions.

Graphical abstract: Determination of partial molar volumes from free energy perturbation theory

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Publication details

The article was received on 14 Nov 2014, accepted on 06 Jan 2015 and first published on 15 Jan 2015


Article type: Paper
DOI: 10.1039/C4CP05304D
Author version available: Download Author version (PDF)
Citation: Phys. Chem. Chem. Phys., 2015,17, 8407-8415
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    Determination of partial molar volumes from free energy perturbation theory

    J. Z. Vilseck, J. Tirado-Rives and W. L. Jorgensen, Phys. Chem. Chem. Phys., 2015, 17, 8407
    DOI: 10.1039/C4CP05304D

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