Theoretical study of methyl hypofluorite (CH sub 3 OF) and related compounds

Journal Article · Sun Dec 01 00:00:00 EST 1991 · Journal of Chemical Physics; (United States)

DOI:https://doi.org/10.1063/1.461326· OSTI ID:5073163

Curtiss, L A ^[1]; Pople, J A ^[2]

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1. Chemical Technology Division/Materials Science Division, Argonne National Laboratory, Argonne, Illinois (USA)
2. Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania (USA)

The Gaussian-2 (G2) theoretical procedure, based on {ital ab} {ital initio} molecular orbital theory, is used to calculate the energies of CH{sub 3}OF, CH{sub 3}OF{sup +}, and related compounds. In this study we have found methyl hypofluorite to have a trans {ital C}{sub {ital 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. {bold 95}, XXX (1991)) and support their interpretation of the photoionization data. The theoretical enthalpy of formation {Delta}{ital H}{sup 0}{sub {ital f}0}(CH{sub 3}OF) of {minus}21.0 kcal/mol is in agreement with the experimental value ({ge}{minus}23.0{plus minus}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 CH{sub 3}OF is OF{gt}HOF{gt}CH{sub 3}OF and the C--O bond strength is 6--8 kcal/mol weaker in methyl hypofluorite than in methanol.

• DOE Contract Number: W-31109-ENG-38
• OSTI ID: 5073163
• Journal Information: Journal of Chemical Physics; (United States), Journal Name: Journal of Chemical Physics; (United States) Vol. 95:11; ISSN JCPSA; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

640302* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Properties & Theory
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL BONDS
ENERGY
FORMATION FREE ENTHALPY
FREE ENTHALPY
MOLECULAR ORBITAL METHOD
MOLECULAR STRUCTURE
ORGANIC COMPOUNDS
ORGANIC FLUORINE COMPOUNDS
ORGANIC HALOGEN COMPOUNDS
PHYSICAL PROPERTIES
STABILITY
THERMODYNAMIC PROPERTIES