1. Rosenstock, Wallenstein, Wahrhaftig, and Eyring, Proc. Natl. Acad. Sci. U.S. 38, 667 (1952).
2. Krauss, Wahrhaftig, and Eyring, Ann. Rev. Nuclear Sci. 5, 241 (1955).ARNUA80066-4243
3. H. M. Rosenstock, Ph.D. thesis, University of Utah (1952).
4. It has been pointed out to us by Professor S. H. Bauer that since the Born‐Oppenheimer approximation for the separation of the electronic vibrational energy is not applicable for short lifetimes, the assumption made by Eyring and co‐workers for the cancellation of the electronic state‐density functions is equivalent to assuming a new set of “average” nuclear modes of vibrations that include the electronic contributions. The state density functions of the reactant species and the activated complex are both described in terms of the “average” nuclear motions and hence will cancel out of the rate equation.2 A possible alternative interpretation is that this assumption requires the distribution of electronic states for the activated complex to be the same as that for the reactant so that, although the reacting species are in different electronic states, they all have approximately the same potential energy barrier (E0). This interpretation would thus modify the definition of E so as to include only the total vibrational energy of the reactant at the instant of reaction, but so that the rate constant is independent of the electronic state in which the reacting molecule‐ion finds itself.
5. W. H. Brubaker, J. Appl. Phys. 26, 1007 (1955).JAPIAU0021-8979