TY - JOUR
T1 - Photodissociation pathways of 1,1-dichloroacetone
AU - Krisch, Maria J.
AU - Bell, M. Justine
AU - FitzPatrick, Benjamin L.
AU - McCunn, Laura R.
AU - Lau, Kai-Chung
AU - Liu, Yi
AU - Butler, Laurie J.
PY - 2007/7/12
Y1 - 2007/7/12
N2 - We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH 3COCHCl 2) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH 3C(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 3C(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 3CO + 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. © 2007 American Chemical Society.
AB - We present a comprehensive investigation of the dissociation dynamics following photoexcitation of 1,1-dichloroacetone (CH 3COCHCl 2) at 193 nm. Two major dissociation channels are observed: cleavage of a C-Cl bond to form CH 3C(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 3C(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 3CO + 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. © 2007 American Chemical Society.
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U2 - 10.1021/jp068208f
DO - 10.1021/jp068208f
M3 - RGC 21 - Publication in refereed journal
SN - 1089-5639
VL - 111
SP - 5968
EP - 5980
JO - The Journal of Physical Chemistry A
JF - The Journal of Physical Chemistry A
IS - 27
ER -