Photodissociation of the trichloromethyl radical: photofragment imaging and femtosecond photoelectron spectroscopy

Abstract

Halogen-containing radicals play a key role in catalytic reactions leading to stratospheric ozone destruction, thus their photochemistry is of considerable interest. Here we investigate the photodissociation dynamics of the trichloromethyl radical, CCl₃ after excitation in the ultraviolet. While the primary processes directly after light absorption are followed by femtosecond-time resolved photoionisation and photoelectron spectroscopy, the reaction products are monitored by photofragment imaging using nanosecond-lasers. The dominant reaction is loss of a Cl atom, associated with a CCl₂ fragment. However, the detection of Cl atoms is of limited value, because in the pyrolysis CCl₂ is formed as a side product, which in turn dissociates to CCl + Cl. We therefore additionally monitored the molecular fragments CCl₂ and CCl by photoionisation at 118.2 nm and disentangled the contributions from various processes. A comparison of the CCl images with control experiments on CCl₂ suggest that the dissociation to CCl + Cl₂ contributes to the photochemistry of CCl₃.