Cross-correlation trajectory study of V--V energy transfer in HF--HF and DF--DF

Journal Article · Wed Oct 15 00:00:00 EDT 1980 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.440591· OSTI ID:5002232

Coltrin, M E; Koszykowski, M L; Marcus, R A

Results of a fully three-dimensional classical trajectory calculation of vibrational energy transfer are presented for the collision of HF(v=1) with HF(v=1) and its deuterium analog. A cross-correlation method, together with quasiclassical trajectories, is introduced to relate the changes in vibrational states of the two molecules to probabilities and rate constants. Multiple collisions are found to make an important contribution to the vibrational energy transfer cross-sections for the present potential surface. Vibrational anharmonicity is shown to decrease the energy transfer rate constant by a factor of ten, by causing the process to be further from exact resonance. Excellent agreement with experiment is obtained for the HF--HF and DF--DF systems.

• Research Organization: Department of Chemistry, University of Illinois, Urbana, Illinois 61801
• OSTI ID: 5002232
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 73:8; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

640304* -- Atomic
Molecular & Chemical Physics-- Collision Phenomena
74 ATOMIC AND MOLECULAR PHYSICS
CLASSICAL MECHANICS
COLLISIONS
CORRELATIONS
CROSS SECTIONS
DATA
DEUTERIUM COMPOUNDS
ENERGY LEVELS
ENERGY TRANSFER
EXCITED STATES
EXPERIMENTAL DATA
FLUORIDES
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROFLUORIC ACID
HYDROGEN COMPOUNDS
INFORMATION
INORGANIC ACIDS
MECHANICS
MOLECULE COLLISIONS
MOLECULE-MOLECULE COLLISIONS
NUMERICAL DATA
THREE-DIMENSIONAL CALCULATIONS
TRAJECTORIES
VIBRATIONAL STATES