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See, for example, P. Armentrout, Acc. Chem. Res. 28, 430 (1995); J. J. Grabowski and J. Lee, Chem. Rev. 92, 1611 (1992); K. E. Sahlstrom, W. B. Knighton, E. P. Grimsrud, J. Phys. Chem. A 101, 5543 (1997); C. J. Torborg, J. J. Rabasco, S. R. Kass, Tetrahedron Lett. 36, 6025 (1995); N. M. M. Nibbering, S. Ingemann, L. J. De Koning, in Structure, Energetics, and Dynamics of Organic Ions, T. Baer, C.-Y. Ng, I. Powis, Eds. (Wiley, New York, 1996); J. M. Riveros, S. M. Jose, K. Takashima, Adv. Phys. Org. Chem. 21, 197 (1985); N. Goldberg and H. Schwarz, Acc. Chem. Res. 27, 347 (1994); R. R. Squires, ibid. 25, 461 (1992); J. V. Seely, R. A. Morris, A. A. Viggiano, H. Wang, W. L. Hase, J. Am. Chem. Soc. 119, 577 (1997).
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There is no "minimum lifetime" necessary to ensure statistical behavior, because the lifetime itself depends to some extent on energy redistribution, and contributions from dynamics in the entrance channel and at the transition state are difficult to predict. There is, however, a relation between the the extent of statistical behavior and the lifetime expected under statistical conditions [K. A. Boering and J. I. Brauman, J. Chem. Phys. 97, 5439 (1992)].
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o, is zero.
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Supported by NSF and fellowships from NSF (to S.L.C. and M. L.C.), the American Chemical Society Division of Organic Chemistry (to S.L.C. and M.L.C.), and the General Electric Fund (C.K.R.).
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