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-particl e master equation. The method leads to an infinite hierarchy for vector cor relation patterns that can be truncated two different ways. The simplest on e reproduces the conventional Integral Encounter Theory (IET), while the ot her allows a general modification of the kernel, resulting in the matrix fo rmulation of so called Modified Encounter Theory (MET). Unlike LET, MET acc ounts for all binary contributions and correctly restores the long-time asy mptotics of bimolecular reactions. The matrix MET, applied in Part II to re versible reactions of inter-molecular energy transfer, significantly improv es the results obtained with other methods. (C) 2000 American Institute of Physics.