Stochastic models for chemical reactions: I. Theory of the unimolecular reaction process

A stochastic model for the basic unimolecular chemical reaction is derived. This model provides a mathematical basis, altogether missing in the current kinetic theory, for the analysis of inherent random fluctuations about the strict concentration-time course prescribed by the existing deterministic theory. Limits on the extent of the predicted inherent variability are obtained and compared with those usually expected purely on the basis of random experimental errors of extraneous origin (not associated with the mechanism of reaction). The results support the extrapolation to chemical systems of a principle of statistical inaccuracy for physical systems which has been called by E. Schroedinger “the Law of Physics.”