UV photodissociation dynamics of allyl radical by photofragment translational spectroscopy

Photodissociation of the allyl radical, CH2CHCH2, has been studied using the method of molecular beam photofragment translational spectroscopy following excitation to the (C) over tilde(2 B-2(1)) and (A) over tilde(1 B-2(1)) states by 248 and 351 nm photons. Two different primary channels have been detected following 248 nm excitation: H-atom loss (84%) and CH3 elimination (16%). From the product translational energy distribution and polarization dependence studies, dissociation processes from the ground-state C3H5 potential energy surface are inferred for both wavelengths. At 248 nm there may also be a contribution to the H-atom loss channel from predissociation by a higher electronically excited state. Rice-Ramsperger-Kassel-Marcus (RRKM) calculations show that the formation of cyclopropene is not important, while formation of allene and methylacetylene from dissociation of 1- and 2-propenyl radicals are important reaction pathways at both wavelengths. Translational energy distributions peaking well away from zero provide evidence for CH3 elimination directly from an allylic structure through a four-member cyclic transition state. (C) 1998 American Institute of Physics. [S0021-9606(98)02137-0].