Photofragmentation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm

Abstract

Translational photofragment spectroscopy has been used to study the photodissociation dynamics of n-C₃H₇I and i-C₃H₇I at 248 nm. The measured anisotropies of the photofragments show that the initial absorption is the (parallel polarized) ³ Q ₀ ← N transition with a dissociation lifetimes of 3·7 ± 2 × 10^-13 s and 2·5 ± 2 × 10^-13 s respectively. The of flight measurements yield the energy disposal for channels leading to I(² P _3/2) and I*(² P _1/2) for both molecules, although with greater uncertainty for i-C₃H₇I. The average energy disposed into translation is 43 per cent (I) and 52 per cent (I*) for n-C₃H₇I, and 39 per cent (I) and 57 per cent (I*) for i-C₃H₇I.

The energy disposal for a variety of alkyl iodides are found to be well described by an impulsive model of the dissociation dynamics with the n-iodoalkanes showing a near constant width for the translational energy distribution regardless of its absolute value. A simple Landau-Zener curve crossing description is used to highlight the substantial change in curve crossing probability caused by substitution at the β carbon or change to a secondary structure for the radical. Finally a model which combines the soft-radical impulse model for energy disposal with the Landau-Zener curve crossing probability is found to provide an excellent description of the I* quantum yields for the n-iodoalkanes.