On the dissociation of aromatic radical anions in solution. 2. Reaction path and rate constant analysis

The theoretical formulation presented for the solution reaction path and rate constant for the radical anion [CN-Phi-Cl].(-) dissociation in solution, described in the preceding paper of this series of work, hereafter referenced as I. The reaction paths that lead to the bent geometry transition state, which is required for the avoidance of the conical intersection point, and cross through such a state vary with the solvent (e.g., water versus acetonitrile) and differ considerably from an equilibrium solvation image. A transition state theory (TST) rate constant, k(TST), is described in terms of reactive and nonreactive normal modes and is contrasted with a conventional equilibrium solvation perspective. Finally, dissipative frictional effects on the reaction rate are examined and determined to be negligible, which supports the use of the k(TST) formula for the rate constant evaluation in I.