Mode specificity in the unimolecular dissociation of formaldehyde (H2CO→H2+CO), a two-mode model

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Abstract
The reaction path (the minimum energy path in mass‐weighted Cartesian coordinates) and all the coupling functions which fully characterize the reaction path Hamiltonian of Miller, Handy, and Adams [J. Chem. Phys. 7 2, 99 (1980)], have been calculated for the unimolecular dissociation of formaldehyde (H2CO→H2+CO) in its ground electronic state. The reaction coordinate and the four other in‐plane vibrational modes are strongly coupled to each other, but the out‐of‐plane vibration is coupled directly only to the reaction coordinate. Calculations of the type of Waite and Miller [J. Chem. Phys. 7 3, 3713 (1980); 7 4, 3910 (1981)] for the state‐specific unimolecular rate constants are carried out for a two‐mode model consisting of the reaction coordinate and the out‐of‐plane vibration, and one observes a significant degree of mode specificity; i.e., the unimolecular rate constant for a given metastable state is not a smooth function of the energy of the state. It is suggested that this mode specificity may persist in the complete six‐mode system.

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