title: Parsing partial molar volumes of small molecules: a molecular dynamics study.
abstract: We used molecular dynamics (MD) simulations in conjunction with the Kirkwood-Buff theory to compute the partial molar volumes for a number of small solutes of various chemical natures. We repeated our computations using modified pair potentials, first, in the absence of the Coulombic term and, second, in the absence of the Coulombic and the attractive Lennard-Jones terms. Comparison of our results with experimental data and the volumetric results of Monte Carlo simulation with hard sphere potentials and scaled particle theory-based computations led us to conclude that, for small solutes, the partial molar volume computed with the Lennard-Jones potential in the absence of the Coulombic term nearly coincides with the cavity volume. On the other hand, MD simulations carried out with the pair interaction potentials containing only the repulsive Lennard-Jones term produce unrealistically large partial molar volumes of solutes that are close to their excluded volumes. Our simulation results are in good agreement with the reported schemes for parsing partial molar volume data on small solutes. In particular, our determined interaction volumes() and the thickness of the thermal volume for individual compounds are in good agreement with empirical estimates. This work is the first computational study that supports and lends credence to the practical algorithms of parsing partial molar volume data that are currently in use for molecular interpretations of volumetric data.
authors.affiliation: Department of Pharmaceutical Sciences, Leslie Dan Faculty of Pharmacy, University of Toronto, Toronto, Ontario, Canada.
authors.forename: Nisha
authors.initials: N
authors.lastname: Patel
authors.forename: David N
authors.initials: DN
authors.lastname: Dubins
authors.forename: Régis
authors.initials: R
authors.lastname: Pomès
authors.forename: Tigran V
authors.initials: TV
authors.lastname: Chalikian
mesh_terms: D000465:Algorithms; D007287:Inorganic Chemicals / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D009930:Organic Chemicals / Q000737:chemistry
chemical_list: D007287:Inorganic Chemicals; D009930:Organic Chemicals