Ultraviolet photodissociation of vinyl iodide: understanding the halogen dependence of photodissociation mechanisms in vinyl halides

The photodissociation of vinyl iodide has been investigated at several wavelengths between 193 and 266 nm using three techniques: time-resolved Fourier transform emission spectroscopy, multiple pass laser absorption spectroscopy, and velocity-mapped ion imaging. The only dissociation channel observed is C-I bond cleavage to produce C2H3 (v, N) + I (P-2(J)) at all wavelengths investigated. Unlike photodissociation of other vinyl halides (C2H3X, X = F, Cl, Br), in which the HX product channel is significant, no HI elimination is observed. The angular and translational energy distributions of I atoms indicate that atomic products arise solely from dissociation on excited states with negligible contribution from internal conversion to the ground state. We derive an upper limit on the C-I bond strength of D-0(C2H3-I) <= 65 kcal mol(-1). The ground-state potential-energy surface of vinyl iodide is explored by ab initio calculations. We present a model in which the highest occupied molecular orbital in vinyl halides has increasing X(np(perpendicular to)) non-bonding character with increasing halogen mass. This change leads to reduced torsional force around the C-C bond in the excited state. Because the ground-state energy is highest when the CH2 plane is perpendicular to the CHX plane, a reduced torsional force in the excited state correlates with a lower rate for internal conversion compared to excited-state C-X bond emission. This model explains the gradual change in photodissociation mechanisms of vinyl halides from the dominance of internal conversion in vinyl fluoride to the dominance of excited-state dissociation in vinyl iodide.