Ab initio molar volumes and gaussian radii

Drew F. Parsons, Barry W. Ninham

    Research output: Contribution to journalArticlepeer-review

    113 Citations (Scopus)

    Abstract

    Ab initio molar volumes are calculated and used to derive radii for ions and neutral molecules using a spatially diffuse model of the electron distribution with Gaussian spread. The Gaussian radii obtained can be used for computation of nonelectrostatic ion-ion dispersion forces that underlie Hofmeister specific ion effects. Equivalent hard-sphere radii are also derived, and these are in reasonable agreement with crystalline ionic radii. The Born electrostatic self-energy is derived for a Gaussian model of the electronic charge distribution. It is shown that the ionic volumes used in electrostatic calculations of strongly hydrated cosmotropic ions ought best to include the first hydration shell. Ionic volumes for weakly hydrated chaotropic metal cations should exclude electron overlap (in electrostatic calculations). Spherical radii are calculated as well as nonisotropic ellipsoidal radii for nonspherical ions, via their nonisotropic static polarizability tensors.

    Original languageEnglish
    Pages (from-to)1141-1150
    Number of pages10
    JournalJournal of Physical Chemistry A
    Volume113
    Issue number6
    DOIs
    Publication statusPublished - 12 Feb 2009

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