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Ab initio molar volumes and gaussian radii
Journal article   Peer reviewed

Ab initio molar volumes and gaussian radii

D.F. Parsons and B.W. Ninham
The Journal of Physical Chemistry A, Vol.113(6), pp.1141-1150
2009
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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.

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Citation topics
2 Chemistry
2.89 Ionic, Molecular & Complex Liquids
2.89.677 Liquid Water
Web Of Science research areas
Chemistry, Physical
Physics, Atomic, Molecular & Chemical
ESI research areas
Chemistry
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