Dynamical Derivation of Eyring Equation and the Second-Order Kinetic Law

Elementary gas-phase reactions of the bimolecular type A + B -> Products are characterized by the second-order kinetic law -d[A]/dt = k[A][B], where [A] and [B] are the concentrations of A and B species, t is the time, and k is the rate constant, usually estimated by means of Eyring equation. Here, we show that its dynamical derivation, as such, is not consistent with the second-order law. This contradiction is however removed by introducing a correlation between what we call potentially reactive pairs. A new presentation of the dynamical derivation of Eyring equation is finally proposed on the basis of the previous findings. (C) 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110: 2355-2359, 2010