Quantum vibrational transition probabilities from real classical trajectories: Symmetric diatom--diatom collisions. [HaHarmonic oscillator quantal motion]
Our previous theory of vibrationally inelastic atom--diatom collisions, which is based on an approximate correspondence between the classical and quantal equations of motion, is extended here to the problem of translational--vibrational and vibrational--vibrational energy transfer in collisions of two identical diatoms. Parameters describing the quantal motion of harmonic oscillators subject to an interaction potential which includes only terms linear and bilinear in the two oscillator coordinates are evaluated from exact classical trajectories for the full potential. The formalism makes it possible to distinguish between the vibrational--vibrational and translational--vibrational energy transfer modes and to isolate the intermode coupling terms. The validity of approximations based on a reduced state basis is easily evaluated. The model results are in generally excellent agreement with exact fully quantal calculations, and they reproduce well the dependence of the transition probabilities for collinear H/sub 2/+H/sub 2/ collisions on the assumed form of the interaction potential. (AIP)
- Research Organization:
- Chemical Dynamics Laboratory, Department of Chemistry, University of Minnesota, Minneapolis, Minnesota 55455
- OSTI ID:
- 7337991
- Journal Information:
- J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 66:1; ISSN JCPSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
COLLISIONS
CRYOGENIC FLUIDS
ELEMENTS
ENERGY LEVELS
ENERGY TRANSFER
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUIDS
HYDROGEN
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
NONMETALS
VIBRATIONAL STATES