Dynamical derivation of Eyring equation and the second‐order kinetic law

Abstract Elementary gas‐phase reactions of the bimolecular type A + B → Products are characterized by the second‐order kinetic law $- {{d[{\rm A}]} \over {dt}} = k[{\rm A}][{\rm B}]$ , 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. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2355–2359, 2010