Photodissociation dynamics of CO3−

Abstract

The dynamics of CO3− photodissociation is studied with a new photodissociation spectrometer that allows kinetic energy-resolved detection of parent ions and photofragments. Kinetic energy release distributions, photodissociation spectra, and the dependence of the photofragment intensity on the laser power and background pressure are presented. Photodissociation of CO3− in the energy range 1.95–2.2 eV leads to CO2+O− fragments, and is found to occur by two distinct mechanisms. These mechanisms involve three electronic states that correlate with CO2+O−—the 2B1 ground state, a 2A1 weakly bound state, and a repulsive 2B2 state. The first mechanism begins with a low cross section 2A1 ← 2B1 transition that gives structure to the spectra. From this intermediate state, a second photon carries the ion to the 2B2 state. Dissociation to the observed photofragments occurs rapidly on the repulsive surface. In this two photon mechanism, at least 20% of the available energy is disposed of in relative translation of photofragments. The second mechanism is also initiated by the 2A1 ← 2B1 transition. Deexcitation of the 2A1 bound state by internal conversion, however, leads to high lying vibrational levels of the ground 2B1 state. These vibrational levels are found to have an enhanced collision-induced dissociation cross section.