An Exact Quantum Study of Vibrational Deactivation by Reactive and Nonreactive Collisions in the Collinear Isotopic H + FH Systems.
Abstract
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. (Author)
Document Details
- Document Type
- Technical Report
- Publication Date
- Aug 01, 1976
- Accession Number
- ADA053639
Entities
People
- Aron Kuppermann
- George C. Schatz
Organizations
- California Institute of Technology