A comparison of quantum, classical, and semiclassical descriptions of a model, collinear, inelastic collision of two diatomic molecules

M. Page, E. S. Oran, J. P. Boris, D. Miller, R. E. Wyatt, Herschel Albert Rabitz, B. A. Waite

Research output: Contribution to journalArticle

8 Scopus citations

Abstract

The collinear dynamics of a model diatom-diatom system is investigated. The collision partners are harmonic oscillators for which the masses and force constants are chosen to correspond to those of the nitrogen and oxygen molecules. The interaction between the molecules arises from a Lennard-Jones 6-12 potential acting between the inside atoms in the collinear system. Quantum mechanical close coupled calculations are performed for several collision energies ranging from 1.0 to 2.25 eV. The state-to-state transition probabilities which are extracted from these calculations are then used as a benchmark for comparison. Semiclassical calculations are performed within the framework of a classical path approximation. A simple scheme to modify the classical path to reflect energy exchange between the collision coordinate and the internal degrees of freedom is found to improve the results. On the whole, the agreement between the semiclassical and the quantum mechanical results is surprisingly good. The classical trajectory calculations correctly display many of the qualitative features of the collisions but the numerical agreement is not as close. Unexpectedly, the classical results do not appear to be improving as the collision energy is increased.

Original languageEnglish (US)
Pages (from-to)5635-5646
Number of pages12
JournalThe Journal of chemical physics
Volume83
Issue number11
DOIs
StatePublished - Jan 1 1985

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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