A theoretical study of the force field for carbon trioxide

J. S. Francisco, I. H. Williams

Research output: Contribution to journalArticle

Abstract

Geometries force constants and harmonic frequencies are calculated for the cyclic (dioxirane) structure of CO3 by ab initio SCF methods using the 3-21G, 3-21G(*). 6-31G and 6-31G* bases calculated frequency shifts for isotopomeric species agree with experiment and lend support to the vibrational assignments of Jacox and Milligan. Earlier arguments for and against the cyclic, cyclic and open structures of CO3, based upon the "physical reasonableness" of valence force constants are shown to be invalid owing to the dependence of conventional "rigid" force constants upon the choice of valence coordinates. The use of "relaxed" force constants as a basis for meaningful comparison of force fields for molecules described by different sets of redundant valence coordinates is demonstrated.

Original languageEnglish
Pages (from-to)373-383
Number of pages11
JournalChemical Physics
Volume95
Issue number3
DOIs
Publication statusPublished - 15 May 1985

ASJC Scopus subject areas

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

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