Production of CH(X(2)PI) from the multiphoton dissociation of CH2CO at wavelengths of 279.3 and 308 nm

S M Ball, G Hancock, Mathew R. Heal

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CH(X 2PI) has been observed by laser-induced fluorescence (LIF) spectroscopy as the product of the two-photon dissociation of ketene (CH2CO) at 279.3 and 308 nm. The nascent distribution of rotational levels is Gaussian in profile, consistent with a 'rotational reflection' principle in the dissociation. Thermodynamic arguments imply a fragmentation pathway to CH + HCO following an initial one-photon absorption to the 1A'' excited state of ketene, a second photon absorption, and dissociation following rearrangement via a formylmethylene isomer. Analysis of A doublets in the LIF spectra shows no orbital alignment of CH produced on photolysis at 279.3 nm, but some propensity for PI (A') symmetry alignment (pi orbital of CH parallel to the plane of rotation) for photolysis at 308 nm.

Original languageEnglish
Pages (from-to)523-531
Number of pages9
JournalJournal of the Chemical Society, Faraday Transactions
Issue number4
Publication statusPublished - 21 Feb 1994

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