Exact quantum study of vibrational deactivation by reactive and nonreactive collisions in the collinear isotopic H + FH systems. Interim report. [H + FH, D + FD, H + FD, D + FH]
Accurate quantum mechanical transition probabilities and rate constants for vibrational deactivation via reactive and nonreactive collisions in collinear H + FH(v), D + FD(v), H + FD(v), and D + FH(v) are presented. In all cases, the reactive inelastic rate constants are larger than the nonreactive ones for the same initial and final vibrational states, but the ratios of these reactive and nonreactive rate constants depend strongly on the vibrational quantum number v and on isotopic composition of the reagents. Nonreactive and reactive transition probabilities for multiquantum jump transitions are generally comparable to those for single quantum transitions. This vibrationally nonadiabatic behavior is a direct consequence of the severe distortion of the diatomic that occurs in a collision on a reactive potential surface, and makes H or D more efficient deactivators of HF or DF than are nonreactive collision partners. Most conclusions are in qualitative and even quantitative agreement with those of Wilkins' three-dimensional quasi-classical trajectory study on the same systems.
- Research Organization:
- California Inst. of Tech., Pasadena (USA). Arthur A. Noyes Lab. of Chemical Physics
- OSTI ID:
- 6586336
- Report Number(s):
- AD-A-053639; CONTRIB-5284
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
DEUTERIUM
ATOM-MOLECULE COLLISIONS
DEUTERIUM COMPOUNDS
FLUORIDES
HYDROFLUORIC ACID
HYDROGEN
DE-EXCITATION
REACTION KINETICS
VIBRATIONAL STATES
ATOM COLLISIONS
COLLISIONS
CRYOGENIC FLUIDS
ELEMENTS
ENERGY LEVELS
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
FLUIDS
FLUORINE COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
INORGANIC ACIDS
ISOTOPES
KINETICS
LIGHT NUCLEI
MOLECULE COLLISIONS
NONMETALS
NUCLEI
ODD-ODD NUCLEI
STABLE ISOTOPES
640304* - Atomic
Molecular & Chemical Physics- Collision Phenomena