The gauche effect. A study of localized molecular orbitals and excited-state geometries in FCH2OH

Saul Wolfe, Luis M. Tel, W. J. Haines, M. A. Robb, I. Csizmadia

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Abstract

Near Hartree-Fock molecular wave functions have been computed for several conformations of fluoromethanol using a contracted Gaussian basis set. The computed potential energy curve for the ground state shows a single minimum which corresponds to the conformation in which the polar CF and OH bonds are gauche. The conformation in which these bonds are anticoplanar is the energy maximum. However, in the lowest lying singlet excited state the anticoplanar conformation is an energy minimum and is more stable than the gauche. The canonical molecular orbitals (CMO) have been localized by the method of Edmiston and Ruedenberg. The group sizes derived from the localized molecular orbitals (LMO) have been correlated with the potential curve associated with rotation along the C-O bond. Analysis of these latter data has provided additional theoretical support for the notion that, in a system containing geminal lone pairs, these jointly behave in a nondirectional manner.

Original languageEnglish
Pages (from-to)4863-4870
Number of pages8
JournalJournal of the American Chemical Society
Volume95
Issue number15
Publication statusPublished - 1973

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Molecular orbitals
Excited states
Conformations
Geometry
Chemical bonds
Wave functions
Potential energy
Ground state

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

The gauche effect. A study of localized molecular orbitals and excited-state geometries in FCH2OH. / Wolfe, Saul; Tel, Luis M.; Haines, W. J.; Robb, M. A.; Csizmadia, I.

In: Journal of the American Chemical Society, Vol. 95, No. 15, 1973, p. 4863-4870.

Research output: Contribution to journalArticle

Wolfe, Saul ; Tel, Luis M. ; Haines, W. J. ; Robb, M. A. ; Csizmadia, I. / The gauche effect. A study of localized molecular orbitals and excited-state geometries in FCH2OH. In: Journal of the American Chemical Society. 1973 ; Vol. 95, No. 15. pp. 4863-4870.
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