Photodissociation of the CH2Cl radical: A high-level ab initio study

Abstract

Photodissociation of the CH2Cl radical is investigated by using high-level multireference configuration interaction ab initio methods, including the spin–orbit coupling. All possible fragmentation pathways, namely, CH2Cl + hν → CH2 + Cl, HCCl + H, and CCl + H2, have been analyzed. The potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distance of each pathway have been calculated. Inclusion of the spin–orbit couplings is found to be crucial because it strongly determines the shape of the curves of the different excited states and, therefore, their photodissociation dynamics behavior. Analysis of the potential curves indicates that the pathways producing CH2 + Cl and HCCl + H can occur through a fast direct dissociation mechanism, while the pathway leading to CCl + H2 involves much slower dissociation mechanisms such as internal conversion between electronic states, predissociation, or tunneling through exit barriers. The main implications are that the two faster channels are predicted to be dominant, while the slower pathway is expected to be very unlikely and rather irrelevant. Appreciable actinic fluxes of solar irradiation are available at stratospheric altitudes where ozone is abundant, in the wavelength range where absorption of the first low-lying excited states of CH2Cl has been observed experimentally. Our results show that in this excitation energy range, the above-mentioned two dominant dissociation pathways are open and then could contribute to stratospheric ozone depletion.