Phase space analysis of formaldehyde dissociation branching and comparison with quasiclassical trajectory calculations.
We investigate the dependence of the branching ratio of formaldehyde dissociation to molecular and radical products on the total energy and angular momentum and the HCO rotational state distributions by using a combination of transition state/Rice-Ramsperger-Kassel-Marcus theory and phase space theory. Comparisons are made with recent quasiclassical trajectory (QCT) calculations [Farnum, J. D.; Zhang, X.; Bowman, J. M. J. Chem. Phys. 2007, 126, 134305]. The combined phase-space analysis is in semiquantitative agreement with the QCT results for the rotational distributions of HCO but is only in qualitative agreement for the branching ratio. Nevertheless, that level of agreement serves to provide insight into the QCT results, which showed suppression of the radical channel with increasing total angular momentum for a fixed total energy.
Farnum
John D
JD
Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, Georgia 30322, USA.
Bowman
Joel M
JM