Sm. Ball et al., PRODUCTION OF CH(X (2)PI) FROM THE MULTIPHOTON DISSOCIATION OF CH2CO AT WAVELENGTHS OF 279.3 AND 308 NM, Journal of the Chemical Society. Faraday transactions, 90(4), 1994, pp. 523-531
Citations number
73
Categorie Soggetti
Chemistry Physical","Physics, Atomic, Molecular & Chemical
CH(X 2PI) has been observed by laser-induced fluorescence (LIF) spectr
oscopy 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' princi
ple 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 dissoci
ation following rearrangement via a formylmethylene isomer. Analysis o
f A doublets in the LIF spectra shows no orbital alignment of CH produ
ced on photolysis at 279.3 nm, but some propensity for PI (A') symmetr
y alignment (pi orbital of CH parallel to the plane of rotation) for p
hotolysis at 308 nm.