Translational Energy of Fragments of Ion Decomposition and Totality of States Functions

Abstract

Translational energies of the fragments of ionic decompositions have been calculated for sets of harmonic oscillators with the totality of states obtained by three methods. Best agreement with experimental values observed by Haney and Franklin was obtained with a direct count of states. Good agreement was also found using the expression of Vestal, Wahrhaftig, and Johnston and the recent modification of it by Tou and Wahrhaftig. Finally, the function derived by Thiele in terms of the generalized Bernoulli polynominals gave lower energies than the observed values. The activated complex was viewed first as having one vibrational degree of freedom transformed into a translational degree of freedom and then as a “loosened” complex in which three degrees are transformed. The excluded modes were determined by a consideration of the reaction and the effect of varying them was examined. In all methods the agreement was improved with the assumption that three degrees of freedom, rather than one, are transformed to translation in the activated complex.