title: Structure of the photochemical reaction path populated via promotion of CF(2)I(2) into its first excited state.
abstract: The photochemical reaction path following the promotion of CF(2)I(2) 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 CF(2)I(2)* species either to the CF(2)I + I radical pair or back to the starting CF(2)I(2) 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(2)I(2).
authors.affiliation: Department of Chemistry and Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, USA.
authors.forename: Patrick Z
authors.initials: PZ
authors.lastname: El-Khoury
authors.forename: Alexander N
authors.initials: AN
authors.lastname: Tarnovsky
authors.forename: Igor
authors.initials: I
authors.lastname: Schapiro
authors.forename: Mikhail N
authors.initials: MN
authors.lastname: Ryazantsev
authors.forename: Massimo
authors.initials: M
authors.lastname: Olivucci