title: Photodissociation pathways of 1,1-dichloroacetone.
abstract: We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH(3)COCHCl(2)) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH(3)C(O)CHCl + Cl and elimination of HCl. The branching between these reaction channels is roughly 9:1. The recoil kinetic energy distributions for both C-Cl fission and HCl elimination are bimodal. The former suggests that some of the radicals are formed in an excited electronic state. A portion of the CH(3)C(O)CHCl photoproducts undergo secondary dissociation to give CH(3) + C(O)CHCl. Photoelimination of Cl(2) is not a significant product channel. A primary C-C bond fission channel to give CH(3)CO + CHCl(2) may be present, but this signal may also be due to a secondary dissociation. Data from photofragment translational spectroscopy with electron impact and photoionization detection, velocity map ion imaging, and UV-visible absorption spectroscopy are presented, along with G3//B3LYP calculations of the bond dissociation energetics.
authors.affiliation: The James Franck Institute and Department of Chemistry, The University of Chicago, Chicago, Illinois 60637, USA.
authors.forename: Maria J
authors.initials: MJ
authors.lastname: Krisch
authors.forename: M Justine
authors.initials: MJ
authors.lastname: Bell
authors.forename: Benjamin L
authors.initials: BL
authors.lastname: Fitzpatrick
authors.forename: Laura R
authors.initials: LR
authors.lastname: McCunn
authors.forename: Kai-Chung
authors.initials: KC
authors.lastname: Lau
authors.forename: Yi
authors.initials: Y
authors.lastname: Liu
authors.forename: Laurie J
authors.initials: LJ
authors.lastname: Butler