화학공학소재연구정보센터
Journal of Physical Chemistry A, Vol.111, No.27, 5968-5980, 2007
Photodissociation pathways of 1,1-dichloroacetone
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 a C-Cl bond to form CH3C(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 CH3C(O)CHCl photoproducts undergo secondary dissociation to give CH3 + C(O)CHCl. Photoelimination of Cl-2 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 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.