Abstract
Nonequilibrium distribution functions for polyatomic molecules undergoing unimolecular reaction are considered. Two limiting cases of activation by collision are investigated: the mechanism of strong impacts, in which each collision with an activated molecule may be regarded as bringing about deactivation; and the diffusion mechanism in which the transition between states is described by the Fokker-Planck equation. An accurate solution of the diffusion equation for the thermal decomposition of a nonlinear triatomic molecule makes it possible to elucidate the kinetics of various reactions in relation to the activation mechansim.
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References
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Nikitin, E.E. The mechanism of activation and nonequilibrium distribution functions in unimolecular reactions. Theor Exp Chem 2, 14–19 (1967). https://doi.org/10.1007/BF00524251
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DOI: https://doi.org/10.1007/BF00524251