Theory of thermal unimolecular reactions at low pressures. III. Superposition of weak and strong collisions
1992; American Institute of Physics; Volume: 97; Issue: 1 Linguagem: Inglês
10.1063/1.463627
ISSN1520-9032
Autores Tópico(s)Spectroscopy and Quantum Chemical Studies
ResumoBiexponential models for collisional energy transfer are formulated representing superimposed weak and strong collisions. Analytical solutions of the master equation for low pressure thermal unimolecular reactions at steady state are derived for such models. Nonequilibrium populations of excited states as well as collision efficiencies βc in the low pressure rate constant differ considerably from the corresponding quantities for simple exponential collision models. The results are analyzed in terms of general expressions of the collision efficiency βc as a function of the average energy transfer quantities 〈ΔE〉 and 〈ΔE2〉.
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