The simplest model for chemical reactions that proceed by unimolecular decomposition in the gas phase is the Lindemann mechanism, in which a substrate S is excited by collisions to a level S* with energy sufficient to cause bond breaking or molecular rearrangement ( 1-3). For large molecules, the time scale for decomposition of S* is sufficiently long that further collisions with the bath molecules can cause deactivation of the excited substrate, thus quenching the reaction process. The overall mech anism can be summarized by the following equations:
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Weston et al. (1992) studied this question.
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