C-Cl Bond Fission, Hcl Elimination, And Secondary Radical Decomposition In The 193 Nm Photodissociation Of Allyl Chloride

The primary photodissociation dynamics of allyl chloride upon excitation at 193 nm is investigated in a crossed laser-molecular beam scattering apparatus. Tunable vacuum ultraviolet ~VUV! photoionization of the products provides a unique ability to learn about the secondary reaction products of the nascent photoproducts formed. The data show evidence for four significant primary reaction channels: a previously unidentified low kinetic energy C–Cl bond fission channel producing unstable allyl radicals, an excited state C–Cl bond fission channel producing Cl atoms with high translational energy, an HCl elimination pathway releasing significant energy to product translation to HCl and its momentum-matched mass 40 partner, and an HCl elimination channel producing low kinetic energy HCl products and predominantly unstable mass 40 products. The measured branching of these primary reaction channels of @all C–Cl# : @fast C–Cl# : @slow C–Cl# : @fast HCl# : @slow HCl# : @all HCl# is 1.00: 0.971: 0.029: 0.291: 0.167: 0.458 ~where fast refers to the high recoil kinetic energy channels!. The high internal energy allyl radicals formed in the slow C–Cl fission pathway of allyl chloride further dissociate/isomerize, as do the unstable mass 40 products formed in the HCl elimination pathways, and these products are investigated. Photoionization efficiency ~PIE! curves of the HCl product suggest that a three-centered elimination mechanism contributes significantly to an observed HCl elimination reaction. © 2002 American Institute of Physics. @DOI: 10.1063/1.1433965#