Mode specificity in unimolecular reaction dynamics: The Henon--Heiles potential energy surface

Journal Article · Wed Apr 01 00:00:00 EST 1981 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.441567· OSTI ID:6438966

Waite, B A; Miller, W H

Energies and lifetimes (with respect to tunneling) for metastable states of the Henon--Heiles potential energy surface (V(x,y) = 1/2x/sup 2/-1/3x/sup 3/+1/2y/sup 2/+xy/sup 2/) have been computed quantum mechanically (via the method of complex scaling). This is a potential surface for which the classical dynamics is known to change from quasiperiodic at low energies to ergodic-like at higher energies. The rate constants (i.e., inverse lifetimes) for unimolecular decay as a function of energy, however, are seen to be well described by standard statistical theory (microcanonical transition state theory, RRKM plus tunneling) over the entire energy region. This is thus another example indicating that mode specificity in unimolecular reaction dynamics is not determined solely by the quasiperiodic/ergodic character of the intramolecular mechanics.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 6438966
• Journal Information: J. Chem. Phys.; (United States), Vol. 74:7
• Country of Publication: United States
• Language: English

Related Subjects

74 ATOMIC AND MOLECULAR PHYSICS
37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
QUANTUM MECHANICS
CHEMICAL REACTION KINETICS
CLASSICAL MECHANICS
ENERGY
LIFETIME
METASTABLE STATES
POTENTIAL ENERGY
SURFACES
ENERGY LEVELS
EXCITED STATES
KINETICS
MECHANICS
REACTION KINETICS
640305* - Atomic
Molecular & Chemical Physics- Atomic & Molecular Theory- (-1987)
400201 - Chemical & Physicochemical Properties