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Roaming is the dominant mechanism for molecular products in acetaldehyde photodissociation

2008; National Academy of Sciences; Volume: 105; Issue: 35 Linguagem: Inglês

10.1073/pnas.0802769105

1091-6490

Brianna R. Heazlewood, Meredith J. T. Jordan, Scott H. Kable, Talitha M. Selby, David L. Osborn, Benjamin C. Shepler, Bastiaan J. Braams, Joel M. Bowman,

Atmospheric chemistry and aerosols

Reaction pathways that bypass the conventional saddle-point transition state (TS) are of considerable interest and importance. An example of such a pathway, termed "roaming," has been described in the photodissociation of H(2)CO. In a combined experimental and theoretical study, we show that roaming pathways are important in the 308-nm photodissociation of CH(3)CHO to CH(4) + CO. The CH(4) product is found to have extreme vibrational excitation, with the vibrational distribution peaked at approximately 95% of the total available energy. Quasiclassical trajectory calculations on full-dimensional potential energy surfaces reproduce these results and are used to infer that the major route to CH(4) + CO products is via a roaming pathway where a CH(3) fragment abstracts an H from HCO. The conventional saddle-point TS pathway to CH(4) + CO formation plays only a minor role. H-atom roaming is also observed, but this is also a minor pathway. The dominance of the CH(3) roaming mechanism is attributed to the fact that the CH(3) + HCO radical asymptote and the TS saddle-point barrier to CH(4) + CO are nearly isoenergetic. Roaming dynamics are therefore not restricted to small molecules such as H(2)CO, nor are they limited to H atoms being the roaming fragment. The observed dominance of the roaming mechanism over the conventional TS mechanism presents a significant challenge to current reaction rate theory.