Abstract
Infrared matrix studies of two conformers ( s-cis and s-gauche) of methylvinylether (MVE) will be reported. Thermal molecular beam spectra with Knudsen cell temperatures up to 925 K yield nearly complete assignments of the fundamentals of both conformers and enthalpy of conversion, Δ H ≈ 6.62(35) kJ/mol. Irradiation of MVE:M (M = Ar, N 2) by 3300–2800 cm −1 radiation (but not by radiation with ν < 1450 cm −1) induces photoconversion of s-cis to the same less stable conformer as produced by thermal beam technique; the conversion is shown to be a one-photon process. Quantum yield of conversion is about three times lower for MVE:N 2 than to MVE:Ar. Highly complex band profiles were found in both matrices. By line shape analysis the band profiles are found to be complex superpositions of near Lorentzian-bands. Intensity of the components are shown to vary either with Knudsen cell temperature or with duration of photoconversion. Line shape analysis is found useful for site structure discrimination and identification of vibrational transitions of the two conformers. Some features of the spectra indicate the less stable conformer to possess gauche r e -structure.
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