Non-adiabatic photodissociation dynamics of vinyl iodide from nσ* and nπ* transitions†

The photodissociation dynamics of vinyl iodide upon photoexcitation at 199.2 and 200 nm are investigated in a joint theoretical and experimental study. The gas-phase absorption spectrum measured by Fourier transform spectroscopy along with the use of synchrotron radiation is reported and a reassignment of the excited electronic states responsible for the absorption at the energy range of interest is proposed. Femtosecond time-resolved velocity map imaging in conjunction with resonance enhanced multiphoton ionization detection of the I(²P_3/2) and I*(²P_1/2) photofragments have been carried out. The experimental results are discussed in view of high-level ab initio calculations including potential energy curves and semiclassical dynamics. Three conical intersections (CIs) governing the dynamics are identified in a search for stationary points using spin–orbit gradients. Based on these results, a complete picture of the photodissociation dynamics of vinyl iodide is obtained. Photoexcitation at 200 nm, associated with a n_I(⊥)σ* transition, leads to a fast dissociation occurring in a repulsive potential energy surface, which is mediated by a CI with a low-lying excited electronic state. This mechanism resembles the typical dissociation of alkyl iodides in the first absorption A-band. In contrast, one-photon excitation at 199.2 nm into a well-defined vibronic structure of the absorption spectrum is assigned to a n_I(‖)π* transition. The subsequent dissociation dynamics from that state features an ultrafast electronic predissociation with sub-200 femtosecond reaction time. State-switching at a first CI with a low-lying electronic state governing the mechanism involves states of completely different character, occurring in less than 20 fs. This remarkably fast process takes place through an initial stretch of the CC bond, followed by a C–I elongation with subsequent vibrational activity in the CC stretch mode.