Monomer–excimer kinetics in solution. II. Statistical nonequilibrium thermodynamic approach

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Abstract
The statistical nonequilibrium thermodynamic theory of diffusion‐influenced reactions is employed to study reversible excimer formation in solution. Three types of rate coefficients for bimolecular excimer formation are discussed: (i) molecular rate coefficients defined by one‐way reactive fluxes, (ii) phenomenological rate constants based on form of the macroscopic rate equations, and (iii) modified, time‐dependent phenomenological rate coefficients. Relations are derived linking: (i) the molecular rate coefficients for reversible and irreversible excimer formation rates, and (ii) the steady‐state molecular rate constant and the Laplace transform of the time resolved irreversible rate coefficient. The relationship between the present approach and the microscopic–stochastic theory of excimer formation is discussed.