Reaction Kinetics in Stochastic Models

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Abstract
Two soluble models of chemical reaction kinetics are treated. It is found that the equilibrium approximation overestimates the true rate constants by a factor that is typically about 2 and may often be much larger. The mathematical mechanism by which a high activation energy is reflected in a long chemical relaxation time is studied and is found to be the same as the mechanism by which, in quantum mechanics, tunneling through a high potential barrier between two wells in resonance leads to a slight separation between the two lowest energy levels.