Journal of Chemical Physics, Vol.114, No.4, 1754-1762, 2001
Integral encounter theories of multistage reactions. I. Kinetic equations
The matrix kinetic equations for multi-stage reactions in liquid solutions are derived using a newly developed original method based on a many-particle master equation. The method leads to an infinite hierarchy for vector correlation patterns that can be truncated two different ways. The simplest one reproduces the conventional Integral Encounter Theory (IET), while the other allows a general modification of the kernel, resulting in the matrix formulation of so called Modified Encounter Theory (MET). Unlike LET, MET accounts for all binary contributions and correctly restores the long-time asymptotics of bimolecular reactions. The matrix MET, applied in Part II to reversible reactions of inter-molecular energy transfer, significantly improves the results obtained with other methods. (C) 2000 American Institute of Physics.