Molecular force fields of octahedral XF6 molecules

Hyunyong Kim, Paul A. Souder, Howard H. Claassen

Research output: Contribution to journalArticlepeer-review

78 Scopus citations


The orbital valency force field (OVFF) is applied to the fifteen hexafluorides whose vibrational frequencies are known, and the best-fit force constants are calculated. The OVFF showed definite advantages over the more widely used UBFF model in that (a) the angular coordinates contain no redundancy; (b) the agreement with the observed frequencies in the angle deformation modes is far superior; and (c) the least squares calculation procedure yields rapidly-converging sets of force constants for all fifteen hexafluorides. The f1u force constants of some of the hexafluorides are determined from their infrared band envelopes and are compared with the calculated values. The angle distortion constant D and the repulsion constant F are found to have strong dependence upon the number of nonbonding electrons in the 4d and 5d transition metal series. This effect is discussed in terms of the repulsion between the nonbonding and bonding electrons and the Coulombic forces between partially ionic fluorine atoms.

Original languageEnglish (US)
Pages (from-to)46-66
Number of pages21
JournalJournal of Molecular Spectroscopy
Issue number1
StatePublished - May 1968
Externally publishedYes

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Spectroscopy
  • Physical and Theoretical Chemistry


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