Mode specificity in the unimolecular dissociation of formaldehyde (H/sub 2/CO. -->. H/sub 2/+CO), a two-mode model

Journal Article · Sat Jan 01 04:00:00 EST 1983 · J. Chem. Phys.; (United States)

OSTI ID:6645798

Waite, B A; Gray, S K; Miller, W H

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. 72, 99 (1980)), have been calculated for the unimolecular dissociation of formaldehyde (H/sub 2/CO..-->..H/sub 2/+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. 73, 3713 (1980); 74, 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.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division, Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 6645798
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 78:1; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
ALDEHYDES
CHEMICAL REACTION KINETICS
COUPLING
DISSOCIATION
ENERGY LEVELS
EXCITED STATES
FORMALDEHYDE
GROUND STATES
KINETICS
ORGANIC COMPOUNDS
OSCILLATION MODES
REACTION KINETICS
VIBRATIONAL STATES