Some new approaches to semiclassical and quantum transition state theory

Conference · Mon Oct 01 04:00:00 EDT 1990

OSTI ID:5618990

Miller, W H

Semiclassical and quantum mechanical transition state theory is reviewed and two new approaches described. One is general implementation of a semiclassical rate expression that involves the good'' action-angle variables associated with the saddle point (i.e., transition state) of a potential energy surface. The other is an evaluation of a formally exact quantum expression for the rate in terms of Siegert eigenvalues associated with the transition state. Siegert eigenvalues are usually associated with scattering resonances, so their identification with the saddle point of a potential surface, and the expression for the reaction rate in terms of them, is quite an unexpected and novel development. 14 refs.

• Research Organization: Lawrence Berkeley Lab., CA (USA)
• Sponsoring Organization: DOE; USDOE, Washington, DC (USA)
• DOE Contract Number: AC03-76SF00098
• OSTI ID: 5618990
• Report Number(s): LBL-29938; CONF-9009383--1; ON: DE91012345
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201 -- Chemical & Physicochemical Properties
657002* -- Theoretical & Mathematical Physics-- Classical & Quantum Mechanics
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
CHEMICAL REACTION KINETICS
EIGENVALUES
ENERGY-LEVEL TRANSITIONS
INELASTIC SCATTERING
KINETICS
MECHANICS
PROBABILITY
QUANTUM MECHANICS
REACTION KINETICS
RESONANCE SCATTERING
SCATTERING
SEMICLASSICAL APPROXIMATION