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

Journal Article · Wed Apr 01 04:00:00 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), Journal Name: J. Chem. Phys.; (United States) Vol. 74:7; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

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