Reaction kinetics beyond rate equations: A correlation-function study of the effects of space dimension and reactant mobilities on the bimolecular annihilation reaction

A novel correlation-function approach, making use of many-particle densities and terminating their hierarchy by employing Kirkwood's superposition principle, is applied to the bimolecular annihilation reaction A+B to O. The roles of initial concentrations, space dimension and ratio of the reactant diffusivities in the modification of the reaction rate by many-particle effects are compared with computer simulations. The many-particle effects cause the reaction A+B to 0 to exhibit spatial self-organization phenomena even in the absence of direct A-A or B-B interactions. It is argued that this result casts serious doubts on the validity of the Hanusse-Tyson-Light theorem in synergetics.