Manifestation of anisotropic reactivity and molecular interactions in chemical reaction kinetics

The effect of highly anisotropic reactivity and interaction between molecul es on kinetics of diffusion-influenced liquid-phase reactions is analyzed i n detail. The Smoluchowski equation (SE) that describes the space/time evol ution of pairs of reacting molecules is solved analytically by the method p roposed earlier [A. I. Shushin, Chem. Phys. Lett. 130, 452 (1986); Chem. Ph ys. 120, 91 (1988)]. The method allows for reducing the original SE in curv ilinear translational/rotational coordinates of reacting molecules to the S E in the local Cartesian coordinates in the vicinity of reactive relative o rientations. Many formulas for the reaction rate are derived in the realist ic models of reactivity using this method. Analysis demonstrates high accur acy of these formulas. The model of reactive patches is shown to give react ion rates that are considerably smaller than those predicted here. Peculiar ities of reaction kinetics for molecules with anisotropic reactivity and in teraction potential are analyzed in detail. Possible applications of the ob tained formulas are briefly discussed. (C) 1999 American Institute of Physi cs.