Standard deviations of chemical reaction rates and validity ranges of the statistical theory.

Validity ranges of the statistical theory of chemical reactions are discussed. On the basis of the quantum mechanical scattering theory, the rate of the chemical reaction of the complex-formation mode is formulated. The interaction matrix elements between resonance states and scattering continua are regarded as stochastic variables. The expectation value of the reaction rate is shown to coincide with the prediction of the conventional statistical theory if the condition of overlapping resonance is fulfilled. The standard deviation is found to be inversely proportional to the number of resonance states involved in the width of the collision energy. High density of vibrational energy levels of the collision complex serves to suppress the standard deviation and to make the statistical theory accurate. The condition for the conventional statistical theory to hit the correct value with probabilities more than 99% is obtained as a relation between the number of vibrational modes and the depth of the potential energy well of the collision complex. [ABSTRACT FROM AUTHOR]