| Abstract
| - We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH3COCHCl2) at 193 nm. Two major dissociation channels are observed: cleavage of aC−Cl bond to form CH3C(O)CHCl + Cl and elimination of HCl. The branching between these reactionchannels is roughly 9:1. The recoil kinetic energy distributions for both C−Cl fission and HCl eliminationare bimodal. The former suggests that some of the radicals are formed in an excited electronic state. A portionof the CH3C(O)CHCl photoproducts undergo secondary dissociation to give CH3 + C(O)CHCl. Photoelimination of Cl2 is not a significant product channel. A primary C−C bond fission channel to give CH3CO +CHCl2 may be present, but this signal may also be due to a secondary dissociation. Data from photofragmenttranslational spectroscopy with electron impact and photoionization detection, velocity map ion imaging, andUV−visible absorption spectroscopy are presented, along with G3//B3LYP calculations of the bond dissociationenergetics.
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