TY - JOUR
T1 - Structure of the photochemical reaction path populated via promotion of CF2i2 into its first excited state
AU - El-Khoury, Patrick Z.
AU - Tarnovsky, Alexander N.
AU - Schapiro, Igor
AU - Ryazantsev, Mikhail N.
AU - Olivucci, Massimo
PY - 2009/10/8
Y1 - 2009/10/8
N2 - The photochemical reaction path following the promotion of CF 2I2 into its lowest-lying excited electronic singlet state has been modeled using ab initio multiconfigurational quantum chemical calculations. It is found that a conical intersection drives the electronically excited CF2I2* species either to the CF2I + I radical pair or back to the starting CF2I2 structure. The structures of the computed relaxation pathways explain the photoproduct selectivity previously observed in the gas phase. Furthermore, the results provide the basis for explaining the condensed-phase photochemistry of CF 2I2.
AB - The photochemical reaction path following the promotion of CF 2I2 into its lowest-lying excited electronic singlet state has been modeled using ab initio multiconfigurational quantum chemical calculations. It is found that a conical intersection drives the electronically excited CF2I2* species either to the CF2I + I radical pair or back to the starting CF2I2 structure. The structures of the computed relaxation pathways explain the photoproduct selectivity previously observed in the gas phase. Furthermore, the results provide the basis for explaining the condensed-phase photochemistry of CF 2I2.
UR - http://www.scopus.com/inward/record.url?scp=70349693943&partnerID=8YFLogxK
U2 - 10.1021/jp902873h
DO - 10.1021/jp902873h
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AN - SCOPUS:70349693943
SN - 1089-5639
VL - 113
SP - 10767
EP - 10771
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -