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Semiclassical calculation for collision induced dissociation

Journal Article · · J. Chem. Phys.; (United States)
DOI:https://doi.org/10.1063/1.433155· OSTI ID:7356329

The classical S-matrix theory of Miller and Marcus has been used to compute collision induced dissociation probabilities (P/sup diss/) for particle--oscillator one dimensional collisions. The continuum of dissociation states was discretized in a straightforward way by confining the oscillator to a suitably large box. From this simple discretization an expression for P/sup diss/ in the limit of an infinite box is derived. Numerical results for a truncated harmonic oscillator with an exponential repulsive interaction with the colliding particle are presented for several masses and potential parameters. The behavior of P/sup diss/ as a function of collision energy, well depth and initial vibrational excitation is studied. The energy profile of P/sup diss/ shows a prominent structure which is directly related to the initial vibrational state of the oscillator. The relative dissociation ''efficiencies'' of the different vibrational levels of the oscillator depend drastically on the collision energy, with highly excited vibrational states being more ''efficient'' dissociation candidates at low (near threshold) energies but with the opposite behavior at higher kinetic energies. The dependence of the dissociation probability on potential parameters and masses is analogous to the trends for a comparable energy transfer process. (AIP)

Research Organization:
Chemistry Department, Indiana University, Bloomington, Indiana 47401
OSTI ID:
7356329
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 65:3; ISSN JCPSA
Country of Publication:
United States
Language:
English