System-bath decomposition of the reaction path Hamiltonian. II. Rotationally inelastic reactive scattering of H+H/sub 2/ in three dimensions

Journal Article · Sat Oct 15 04:00:00 EDT 1983 · J. Chem. Phys.; (United States)

OSTI ID:5597716

Schwartz, S D; Miller, W H

Earlier work of the authors (J. Chem. Phys. 77, 2378 (1982)) has shown how the reaction path Hamiltonian of Miller, Handy, and Adams (J. Chem. Phys. 72, 99 (1980)) can be divided into a ''system'' of the reaction coordinate and modes strongly coupled to it, plus a ''bath'' of more weakly coupled modes. Quantum mechanical perturbation theory was used to show how one can combine an exact description of the system dynamics with an approximate (perturbative) treatment of the effect of the bath. The present paper applies this approach to the 3d H+H/sub 2/ reaction, where the two collinear degrees of freedom constitute the system, and the two bending modes the bath. Comparison with the accurate scattering calculations of Schatz and Kupermann (J. Chem. Phys. 65, 4668 (1976)) shows it to provide a good description of the coupling between bending (i.e., rotational) and collinear modes.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 5597716
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 79:8; 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
CHEMICAL REACTIONS
COLLISIONS
ELEMENTS
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
HAMILTONIANS
HYDROGEN
MATHEMATICAL OPERATORS
MOLECULE COLLISIONS
NONMETALS
QUANTUM OPERATORS
ROTATIONAL STATES