Theory of collisional equilibration of a radiatively excited molecular gas

P. G. Harper

Research output: Contribution to journalArticlepeer-review


A theory for the statistical equilibration of the degenerate vibrational modes of a polyatomic molecule is presented. It is shown how combined radiative and bimolecular collisional development of the degenerate multimode system may be related to that of the single-mode system. Exact multimode rate equations are derived and used to demonstrate that for the ideal harmonic system only transient disturbances of quasithermal equilibrium are permitted. A model theory for the truncated harmonic system in terms of rate equations for the first and second population distribution moments is studied. A solution is presented and related to recent experimental studies of cyclobutanone.

Original languageEnglish
Article number015
Pages (from-to)3787-3796
Number of pages10
JournalJournal of Physics B: Atomic and Molecular Physics
Issue number20
Publication statusPublished - 1983


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