THEORETICAL-STUDY OF METHYL HYPOFLUORITE (CH3OF) AND RELATED-COMPOUNDS

The Gaussian-2 (G2) theoretical procedure, based on ab initio molecular orbital theory, is used to calculate the energies of CH3 OF, CH3 OF+, and related compounds. In this study we have found methyl hypofluorite to have a trans C(s) structure and to be stable with respect to loss of fluorine by 45.9 kcal/mol. The energies of fragmentation processes of methyl hypofluorite calculated from G2 theory are in agreement with those measured by Ruscic, Appelman, and Berkowitz [J. Chem. Phys. 95, 7957 (1991)] and support their interpretation of the photoionization data. The theoretical enthalpy of formation DELTA-H(f0)0 (CH3OF) of - 21.0 kcal/mol is in agreement with the experimental value (greater-than-or-equal-to 23.0 +/- 0.7 kcal/mol) derived from the photoionization data. The ordering of the O-F bond strengths in the series of molecules OF, HOF, and CH3 OF is OF > HOF > CH3 OF and the C-O bond strength is 6-8 kcal/mol weaker in methyl hypofluorite than in methanol.