Discussion of ka E

The rate constant ka(E) of Equation 14.3 is the rate constant which is calculated by transition state theory. Analogously to the discussion in Chapter 4 of conventional transition state theory, where chemical equilibrium is between reactants and transition state, it will be assumed here that an equilibrium exists between A (excited A molecules with vibrational energy E, equal to or larger than Eo, the minimum 

In Equations 14.20 through 14.22, Ev refers to the 3N — 6 vibrational degrees of the excited molecule, Ev refers to the 3N — 7 vibrational degrees of freedom of the transition state, E0 is the minimum energy (in excess of the ground state) required for reaction, and x refers to the energy of the particle in the box motion which replaces the imaginary frequency of the transition state. 

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