Mode specificity in unimolecular reaction dynamics

Technical Report · Thu Jul 01 04:00:00 EDT 1982

DOI:https://doi.org/10.2172/6715449· OSTI ID:6715449

Waite, B A

Theoretical studies on mode specificity in unimolecular reaction dynamics are presented, based on essentially exact quantum mechanical methods, a semi-classical multichannel branching model, and classical trajectory methods. The principal aim is to discover the relevant factors governing whether a unimolecular system exhibits mode specificity in its individual state rate constants, i.e., whether quasi-degenerate metastable states decay with significantly different rates. Model studies of two nonlinearly coupled oscillators (one of which can dissociate) demonstrate the effects of various features of potential energy surfaces on the character of the rates (e.g., degeneracy of modes, reaction path curvature, frequency modulation, etc.). These results and those obtained for the Henon-Heiles potential energy surface indicate and apparent absence of correlation between the quasi-periodic/ergodic motion of classical mechanics and the mode specific/statistical behavior of the unimolecular rate constants.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 6715449
• Report Number(s): LBL-14719; ON: DE83001932
• Country of Publication: United States
• Language: English

Related Subjects

640305* -- Atomic
Molecular & Chemical Physics-- Atomic & Molecular Theory-- (-1987)
74 ATOMIC AND MOLECULAR PHYSICS
ALDEHYDES
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
DISSOCIATION
ENERGY LEVELS
EXCITED STATES
FORMALDEHYDE
KINETICS
MATHEMATICAL MODELS
MATRICES
MECHANICS
METASTABLE STATES
MOLECULAR MODELS
MOLECULES
ORGANIC COMPOUNDS
QUANTUM MECHANICS
REACTION KINETICS
S MATRIX
SYMMETRY