Electronic Degrees of Freedom in Classical Mechanics

摘要

Electronic degrees of freedom are generally considered purely a quantum mechanical phenomenon not treatable within the framework of classical mechanics. It is shown that this statement is not true. A classical analog for electronic degrees of freedom developed my Miller (JCP 72, 2272(1980)) is shown to correctly describe Stuekelberg oscillations and electronic-vibrational and rotational resonance phenomenon, strictly quantum mechanical processes, within a classical Hamiltonian framework. Calculations are presented for F* and Br* reaction with H sub 2 in gas phase. A semiclassical model for electronic transitions developed by Miller and George (JCP 56, 5637(1972)) is coupled with both a Langevin model and a Generalized Langevin model and shown to correctly describe electronic dynamics in iodine recombination in a solvent. The results obtained are in good agreement with experiment. (ERA citation 09:023920)