Two-photon photolysis of CF3Cl at 10.5 eV: determination of the Cl*/Cl spin–orbit branching ratio and the formation of electronically excited CF3*

The (5e)−1 4p Rydberg state of CF3Cl at about 10.5 eV has been excited by a two-photon absorption process. The photodissociation into the individual spin states Cl*(2P1/2) and Cl(2P3/2) has been monitored together with the formation of electronically excited CF3*. These fragments were detected by (2+1)REMPI(Cl) or photoionzation (CF3*). The state distribution ratio R=Cl∗/(Cl∗+Cl) was determined to be 0.10±0.05, which is significantly non-statistical.