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Importance of Accurate Dynamic Polarizabilities for the Ionic Dispersion Interactions of Alkali Halides

Parsons, Drew; Ninham, Barry

Description

Ab initio quantum mechanical calculations of the dynamic polarizability of alkali metal and halide ions are performed as a function of imaginary frequency. Electron correlation is shown to provide a significant correction to ionic polarizabilities. Ab initio ion-surface dispersion coefficients are compared, with single- and multimode London approximations. The commonly employed single-mode model with the characteristic frequency taken from the ionization potential of the ion is shown to be...[Show more]

dc.contributor.authorParsons, Drew
dc.contributor.authorNinham, Barry
dc.date.accessioned2015-12-10T22:27:28Z
dc.identifier.issn0743-7463
dc.identifier.urihttp://hdl.handle.net/1885/54219
dc.description.abstractAb initio quantum mechanical calculations of the dynamic polarizability of alkali metal and halide ions are performed as a function of imaginary frequency. Electron correlation is shown to provide a significant correction to ionic polarizabilities. Ab initio ion-surface dispersion coefficients are compared, with single- and multimode London approximations. The commonly employed single-mode model with the characteristic frequency taken from the ionization potential of the ion is shown to be inadequate, underestimating dispersion forces with an average error around 40% or as high as 80% for halide ions. Decomposition of the polarizability data into five modes covers the major modes of each ion adequately (four modes for Li+). Illustrative calculations of surface potentials at the mica surface in aqueous alkali halide electrolytes are made. Charge reversal is obtained with the more polarizable cations, K+ and Rb +. The error in the single-mode ionization potential models is seen as a strong shift in the surface potential from negative toward positive values.
dc.publisherAmerican Chemical Society
dc.sourceLangmuir
dc.subjectKeywords: Ab initio; Average errors; Characteristic frequencies; Charge reversal; Dispersion force; Dynamic polarizabilities; Halide ions; Imaginary frequency; Ionic dispersion; Ionic polarizabilities; Mica surfaces; Multimodes; Polarizabilities; Polarizable cation
dc.titleImportance of Accurate Dynamic Polarizabilities for the Ionic Dispersion Interactions of Alkali Halides
dc.typeJournal article
local.description.notesImported from ARIES
local.identifier.citationvolume26
dc.date.issued2010
local.identifier.absfor020201 - Atomic and Molecular Physics
local.identifier.absfor030701 - Quantum Chemistry
local.identifier.absfor030603 - Colloid and Surface Chemistry
local.identifier.ariespublicationu9210271xPUB294
local.type.statusPublished Version
local.contributor.affiliationParsons, Drew, College of Physical and Mathematical Sciences, ANU
local.contributor.affiliationNinham, Barry, College of Physical and Mathematical Sciences, ANU
local.description.embargo2037-12-31
local.bibliographicCitation.issueOnline 2009
local.bibliographicCitation.startpage1816
local.bibliographicCitation.lastpage1823
local.identifier.doi10.1021/la902533x
dc.date.updated2016-02-24T11:55:38Z
local.identifier.scopusID2-s2.0-75749087645
local.identifier.thomsonID000273831700074
CollectionsANU Research Publications

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