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Science 6 June 1997:
Vol. 276. no. 5318, pp. 1536 - 1538
DOI: 10.1126/science.276.5318.1536
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Reports

Perturbed Equilibria and Statistical Energy Redistribution in a Gas-Phase SN2 Reaction

Stephen L. Craig, John I. Brauman *

The relative translational energy of one set of reactants in the gas-phase equilibrium between chloride ion and chloroacetonitrile 35Cl- + 37ClCH2CN right-left-harpoons  37Cl- + 35ClCH2CN is varied without affecting the energy distribution of the other set. The steady-state ratio of ionic isotopes changes so that there is an increase in the concentration of energized reactants. The ratio provides a measure of the translational energy dependence of the rate constant for the bimolecular nucleophilic substitution (SN2) reaction. The observed energy dependence is indistinguishable from that predicted by Rice-Ramsperger-Kassel-Marcus theory, suggesting that the increased translational energy redistributes statistically in the collision complex.

Department of Chemistry, Stanford University, Stanford, CA 94305-5080, USA.
*   To whom correspondence should be addressed.

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THIS ARTICLE HAS BEEN CITED BY OTHER ARTICLES:
Imaging Nucleophilic Substitution Dynamics.
J. Mikosch, S. Trippel, C. Eichhorn, R. Otto, U. Lourderaj, J. X. Zhang, W. L. Hase, M. Weidemuller, and R. Wester (2008)
Science 319, 183-186
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Steric Effects and Solvent Effects in Ionic Reactions.
C. K. Regan, S. L. Craig, and J. I. Brauman (2002)
Science 295, 2245-2247
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