Computation of Statistical Complexions as Applied to Unimolecular Reactions

Abstract

A method for the exact counting of statistical complexions based on a treatment by Fowler is suggested. In any such calculation for all complexions up to an energy E, a maximum energy E_T is set in the interest of economy of time, beyond which an analytical function must be employed to obtain higher states. The commonly used function of Marcus and Rice is still too approximate unless E_T is made exhorbitantly large and hence a new function is given which allows terminating the exact calculation at a reasonable energy and thus cut the value of E_T by a factor of 3 or 4. Some monoenergetic reactions may proceed at an energy greater than E_T above the activated complex, in this case a simple form of the complexion expression may be used directly in the formulation of a rate constant.