The S(N)1 ionizations RI-->R(+) + I- of tert-butyl iodide and isopropyl iodide are investigated in several solvents theoretically. An electronically coupled two valence bond state solute representation, combined with a (quantum) dielectric continuum solvent description, is employed to generate free energy surfaces in terms of an internuclear separation coordinate r and a collective solvent coordinate s. General free energy surface characteristics are discussed, including transition state energetic, structure, and location features. Decreasing transition state solvent stabilization with increasing solvent polarity is found, in contrast to the conventional Hughes-Ingold perspective, but in agreement with the Hammond postulate. In addition to exhibiting ionization barriers along the nuclear separation coordinate r, these alkyl iodides also have solvent barriers along the solvent coordinate s in the saddle point vicinities. Due to their presence, the rate constant kappa for the alkyl iodide ionization is quite dependent upon the approach used to compute it. Three different rate constants are examined : the harmonic and anharmonic (i.e. including reaction path curvature) rate constants in a solution reaction path description and the rate constant associated with the conventional potential of mean force perspective. There are rather large reaction path curvatures, but, despite this, there is only a mild effect on the reaction rate constant. However, due to the solvent barriers, the potential of mean force perspective gives a rate inaccurate by 1.5-3 orders of magnitude. Thus, the S(N)1 ionizations of t-BuI and i-PrI provide examples where conventional equilibrium solvation reaction rate methods cannot be applied; the ionization process is fundamentally a nonequilibrium one. A related feature is responsible for the breakdown of Grote-Hynes theory in one standard form due to the inapplicability of its underlying assumptions.