Classical models for electronic degrees of freedom: Derivation via spin analogy and application to F*+H/sub 2/. -->. F+H/sub 2/

Journal Article · Sat Sep 01 04:00:00 EDT 1979 · J. Chem. Phys.; (United States)

OSTI ID:6092394

Meyer, H; Miller, W H

By invoking the formal equivalence of a finite level quantum mechanical system to a quantum spin in an external field, this paper shows how a classical model can be constructed for an arbitrary finite level quantum system. For two-state and three-state cases this leads to the same classical Hamiltonian that was obtained earlier by other more heuristic methods, but it shows how to treat the general F-state case. The purpose of this overall approach is to be able to represent the electronic states in electronically nonadiabatic collision processes by a classical degree of freedom so that all degrees of freedom, electronic and heavy particle (i.e., translation, rotation, and vibration) can be treated on a consistent dynamical footing. Application of this model to the quenching of F* (/sup 2/P/sub 1/2/) by collisions with H/sub 2/ is described, and this completely classical approach is seen to give excellent agreement with the quantum mechanical coupled channel calculations of Rebentrost and Lester.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, University of California, Berkeley California 94720
• OSTI ID: 6092394
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 71:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
ATOM COLLISIONS
ATOM-MOLECULE COLLISIONS
CLASSICAL MECHANICS
COLLISIONS
CRYOGENIC FLUIDS
DE-EXCITATION
ELECTRONIC STRUCTURE
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUIDS
FLUORINE
HALOGENS
HYDROGEN
MATHEMATICAL MODELS
MECHANICS
MOLECULE COLLISIONS
NONMETALS
RADIATIONLESS DECAY