The anharmonic potential energy surface of methyl fluoride.
A large experimental spectroscopic data set sensitive to the cubic anharmonic potential energy surface (PES) of methyl fluoride has been compiled from the literature for six symmetric and asymmetric top isotopomers of methyl fluoride: 12CH3F, 13CH3FF, 12CD3F, 13CD3F, 12CHD2F and 12CH2DF. This empirical data set has been used to critically assess the best available literature ab initio cubic force field and various 'improved' theoretical force fields. A perturbation-resonance approach to the calculation of the observables from the force constants has been utilized and existing PESs were found to reproduce the data poorly. The careful treatment required for the correct theoretical reproduction of empirical spectroscopic constants arising from highly correlated least-squares fits to the original data is discussed. A new fit to the data has been performed (optimising 19 of the 38 cubic force constants) resulting in a much improved PES. The latter has been used to predict currently unknown spectroscopic constants for the least well-characterised isotopomer 12CH2DF. The prospects for a future empirical determination of the complete cubic force field of methyl fluoride are discussed and new data most likely to yield new information on the PES identified.
Atkinson
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Department of Chemistry, University of Aberdeen, Old Aberdeen, UK.
Law
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D055598:Chemical Phenomena; D002627:Chemistry, Physical; D006845:Hydrocarbons, Fluorinated / Q000032:analysis / Q000737:chemistry*; D016018:Least-Squares Analysis; D008962:Models, Theoretical; D013055:Spectrophotometry, Infrared / Q000379:methods*
D006845:Hydrocarbons, Fluorinated; C029999:fluoromethane