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J Phys Chem A. 2008 Oct 2;112(39):9344-51. doi: 10.1021/jp802331t. Epub 2008 Jul 3.

"Roaming" dynamics in CH3CHO photodissociation revealed on a global potential energy surface.

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  • 1Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.


We present a quasiclassical trajectory study of the photodissociation of CH3CHO to molecular and radical products, CH4 + CO and CH3 + HCO, respectively, using global ab initio-based potentials energy surfaces. The molecular products have a well-defined potential barrier transition state (TS) but the dynamics exhibit strong deviations from the TS pathway to these products. The radical products are formed via a variational TS. Calculations are reported at total energies corresponding to photolysis wavelengths of 308, 282, 264, 248 and 233 nm. The results at 308 nm focus on a comparison with experiment [Houston, P. L.; Kable, S. H. Proc. Natl. Acad. Sci. U.S.A. 2006, 103, 16079] and the elucidation of the nature and extent of non-TS reaction dynamics to form the molecular products, CH4 + CO. At the other wavelengths the focus is the branching ratio of these products and the radical products, CH3 + HCO.

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