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Pressure effects on bimolecular recombination and unimolecular dissociation reactions
1.R. G. Gilbert and S. C. Smith, Theory of Unimolecular and Recombination Reactions (Blackwell Scientific, Boston, 1990), and references cited therein. Section (6.10) for unimolecular reactions prompted the J-averaging used in Eq. (3.2).
2.K. A. Holbrook, M. J. Pilling, and S. H. Robertson, Unimolecular Reactions (Wiley, New York, 1996), 2nd ed., and references cited therein.
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11.Reference 2, Chap. 9.
12.Y.-Q. Gao and R. A. Marcus (unpublished).
13.Y.-Q. Gao and R. A. Marcus (unpublished).
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14.Ref. 2, Chap. 7, and references cited therein.
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20.There is very little difference whether one sets as in Eq. (2.7), or sets This fact is most easily seen for the unimolecular reaction and we return to this point in Ref. 21.
21.Given in Eq. (2.21), we can explore its consequences for We have, using Eq. (2.15), But the first term equals i.e., which is typically small relative to the individual terms enhancing or decreasing in the rate expression (2.21). Accordingly, typically equals zero to a good approximation.
22.The total collision frequency ω of an ozone molecule in state n is where the 0 label indicates the possibility that there is no net energy transfer. We note in passing that the approximation that in the neighborhood of can be treated as constant while obeys Eq. (3.4) can have some implications for the behavior of ω.
23.We have We write as where Here, (in turn, a shorthand for ) is the vibrational energy and so is the vibrational density of states. Then writing as and integrating over one obtains which can be rewritten as i.e., as as in the text.
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