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 , 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. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2355–2359, 2010