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Vibrational overtone excitation of tetramethyldioxetane in a free jet expansion creates a nearly monoenergetic ensemble of molecules for which the unimolecular reaction rate is directly measured by monitoring the temporal evolution of the electronically excited acetone formed in the reaction. The measurement for the 5νCH vibrational overtone transition determines the unimolecular reaction rate constant at one energy. It is possible to adjust the parameters in the RRKM calculation of the rate constant to obtain agreement with this nearly monoenergetic measurement and to average the calculated energy dependent rate constant over a thermal distribution of initial vibrational energies for comparison with data on room temperature samples. The calculation reproduces the growth of the chemiluminescence following excitation of two CH stretching transitions 4νCH and 5νCH and of a combination transition involving the methyl deformation 4νCH +νdef.
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McGinley et al. (1986) studied this question.
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