Classical probability matrix: Prediction of quantum-state distributions by a moment analysis of classical trajectories

✍ Scribed by Donald G. Truhlar; James W. Duff

• Publisher: Elsevier Science
• Year: 1975
• Tongue: English
• Weight: 350 KB
• Volume: 36
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(75)80302-2

✦ Synopsis

A new method is presented for extractin g approkimnte quantum mechanical state-to-state transition probabilities from the results of classical trajecrory calculations.

Tke method recognizes quantum discreteness by dealing with the quantum mechanical probability matrix, but all dynamical quantities are evaluated by classical mechanics. It is illustrated by applicatier? to the linear atom-diatom collision (vibrational excitation); it is capable of treating both classically allowed and ciassicaily forbidden processes.

It is generally recognized that many of the basic features of molecular collision processes are contained in a classical mechanical treatment of the internuclear motion. We consider the simple example of the nonreactive collision of a diatomic molecule with vibrational quantum number H and an atom, constrained so that a!1 three atoms lie on a line, but it should be fairly clear how the discussion generalizes to vibrational-rotational distributions in general bimolecular inelastic and reactive coilisions. The commonly