Manifestation of macroscopic correlations in elementary reaction kinetics. I. Irreversible reaction A+A→product.

Using an modern many-particle method for the derivation of non-Markovian binary kinetic equations, we have treated theoretically the applicability of the encounter theory (ET) (the prototype of the collision theory) concepts to the widely known diffusion assisted irreversible bulk reaction A+A→product (for example, radical reaction) in dilute solutions. The method shows that the agreement with the ET is observed when the familiar integral ET is employed which in this method is just a step in the derivation of kinetic equations. It allows for two-particle correlations only, but fails to take account of correlation of reactant simultaneously with the partner of the encounter and the reactant in the bulk. However, the next step leading to the modified ET under transformation of equations to the regular form both extends the time range of the applicability of ET rate equation (as it was for reactions proceeding with one of the reactants in excess), and gives the equation of the generalized ET. In full agreement with physical considerations, this theory reveals macroscopic correlations induced by the encounters in the reservoir of free walks. This means that the encounters of reactants in solution are correlated on a rather large time interval of the reaction. Though any nonstationary (non-Markovian) effects manifest themselves rather weakly in the kinetics of the bimolecular reaction in question, just the existence of the revealed macroscopic correlations in the binary theory is of primary importance. In particular, it means that the well-known phenomena which are generally considered to be associated solely with correlation of particles on the encounter (for example, chemically induced dynamic nuclear polarization) may be induced by correlation in the reservoir of free random walks of radicals in solution. [ABSTRACT FROM AUTHOR]