System-bath decomposition of the reaction path Hamiltonian for polyatomic scattering: Quantum perturbative treatment

Journal Article · Wed Sep 01 04:00:00 EDT 1982 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.444159· OSTI ID:5023048

Miller, W H; Schwartz, S

An approach to quantum mechanical reactive scattering in polyatomic molecular systems is described. The formulation is based on the reaction path Hamiltonian of Miller, Handy, and Adams (J. Chem. Phys. 72, 99 (1980)). The essential physical idea is that the reaction coordinate in even polyatomic systems may be coupled strongly to only a few (one or two) of the vibrational modes orthogonal to it, and rather weakly coupled to the (perhaps many) remaining modes. This leads naturally to a ''system-bath'' decomposition of the reaction process, and this paper shows how this is carried through for the reaction path Hamiltonian. If only one transverse mode is included with the reaction coordinate to form the ''system,'' for example, then the overall model is that of a collinearlike reaction, whose dynamics are treated accurately, taking place in a (harmonic) ''bath'' to which it is weakly coupled.

• Research Organization: Department of Chemistry and Materials and Molecular Research Division of the Lawrence Berkeley Laboratory, University of California, Berkeley, California 94720
• OSTI ID: 5023048
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 77:5; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
CHEMICAL REACTIONS
COLLISIONS
HAMILTONIANS
MATHEMATICAL OPERATORS
MECHANICS
MOLECULES
PERTURBATION THEORY
POLYATOMIC MOLECULES
QUANTUM MECHANICS
QUANTUM OPERATORS
THREE-DIMENSIONAL CALCULATIONS