Structural and spectral consequences of ion pairing: A theoretical study of CF3O-Li+ and CF3O-Na+

J. S. Francisco, I. H. Williams

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Ion pairs CF3O-Li+ and CF3O-Na+ are predicted, by ab initio MO calculations at the 3-21G level of SCF theory, to be stable with respect to dissociation or decomposition and to prefer bidentate structures. The essential features of the infrared spectrum of triflouromethoxide anion are well reproduced by the calculations, particularly the ion-pairing induced splitting of degenerate modes as observed for matrix-isolated, as compared with crystalline, CF3O- Cs+. Polarization of the anion by the cation in a bidentate interaction is the major cause of these spectral splittings; the role of covalency is minor and diminishes as the size of the cation increases. Structural and spectral consequences of ion pairing are accounted for simply by changes in hyperconjugative delocalization of oxygen lone-pair electron density into CF-antibonding orbitals.

Original languageEnglish
Pages (from-to)105-114
Number of pages10
JournalChemical Physics
Issue number1
Publication statusPublished - 15 Aug 1985

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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