State resolved photofragmentation of Ni(CO)4 at 193, 248, and 308 nm: A detailed study of the photodissociation dynamics

Abstract

The vibrational, rotational, and translational energy distributions for the CO photofragments from the 193, 248, and 308 nm photolysis of Ni(CO)4 in a supersonic molecular beam have been determined by vacuum ultraviolet laser-induced fluorescence. The measured product energy distributions appeared to be statistical, with equilibrium between the degrees of freedom investigated. The distributions were significantly colder than those calculated with a microcanonical statistical model using published bond energies. To model the measured distributions, it was necessary to postulate that the unsaturated nickel carbonyl products are formed in a stable electronically excited state. By using an excited state energy consistent with published fluorescence experiments, excellent agreement was obtained between the measured distributions and those calculated using a microcanonical statistical model. These results indicate that for 193 nm photolysis, essentially all of the Ni(CO)n products are electronically excited, with about 2.8 eV of electronic excitation. The Ni(CO)n products from 248 nm photolysis are formed in both the ground and excited states, with a 3:1 branching ratio. The data taken at 308 nm also indicate the presence of both channels, with the excited state channel still important. These results are consistent with predictions of earlier ab initio work, although the detailed mechanism is somewhat different. This earlier work is discussed in light of the present results.