Photodissociation of van der Waals complexes of iodine X–I₂ (X = I₂, C₂H₄) via charge-transfer state: A velocity map imaging investigation

The photodissociation of van der Waals complexes of iodine X–I₂ (X = I₂, C₂H₄) excited via Charge-Transfer (CT) band has been studied with the velocity map imaging technique. Photodissociation of both complexes gives rise to translationally “hot” molecular iodine I₂ via channels differing by kinetic energy and angular distribution of the recoil directions. These measured characteristics together with the analysis of the model potential energy surface for these complexes allow us to infer the back-electron-transfer (BET) in the CT state to be a source of observed photodissociation channels and to make conclusions on the location of conical intersections where the BET process takes place. The BET process is concluded to provide an I₂ molecule in the electronic ground state with moderate vibrational excitation as well as X molecule in the electronic excited state. In the case of X = I₂, the BET process converts anion I₂⁻ of the CT state into the neutral I₂ in the repulsive excited electronic state which then dissociates promptly giving rise to a pair of I atoms in the fine states ²P_1/2. In the case of C₂H₄–I₂, the C₂H₄ molecules appear in the triplet T₁ electronic state. Conical intersection for corresponding BET process becomes energetically accessible after partial twisting of C₂H₄⁺ frame in the excited CT state of complex. The C₂H₄(T)–I₂ complex gives rise to triplet ethylene as well as singlet ethylene via the T-S conversion.