Journal of Physical Chemistry, Vol.99, No.15, 5389-5401, 1995
Equilibration in Reversible Bimolecular Reactions
Fast reversible pseudo-unimolecular reactions do not approach equilibrium in the simple exponential fashion predicted by chemical rate equations. Many body effects in bimolecular reactions have been revealed in an extensive series of Brownian simulations, showing up to three distinct phases in the approach to equilibrium. Recent theoretical developments are compared with the simulation as well as with experimental data concerning the pH effect in excited-state proton transfer to solvent.
Keywords:MONOMER-EXCIMER KINETICS;DIFFUSION-INFLUENCED REACTIONS;PROTON-TRANSFER REACTIONS;LONG-TIME BEHAVIOR;GEMINATE RECOMBINATION;NONSTATIONARY DIFFUSION;CONVOLUTION KINETICS;CHEMICAL-REACTIONS;BROWNIAN DYNAMICS;RATE COEFFICIENTS