Publications [#232228] of Stephen L Craig

Journal Articles

1. Craig, SL; Brauman, JI, Perturbed equilibria and statistical energy redistribution in a gas- phase S(N)2 reaction, Science, vol. 276 no. 5318 (June, 1997), pp. 1536-1538, American Association for the Advancement of Science (AAAS) [doi]
   (last updated on 2026/01/16)

   Abstract:
   The relative translational energy of one set of reactants in the gas- phase equilibrium between chloride ion and chloroacetonitrile ³⁵Cl^- + ³⁷ClCH2CN ⇆ 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 (S(N)2) 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.