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Journal Of Chemical Physics


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. (C) 2002 American Institute of Physics.


This work is freely available courtesy of the American Institute of Physics.