Protonation enthalpies in fluorosulfonic acid using ab initio self-consistent reaction field theory

Electrostatic solvation free energies were computed for several small neutral bases and their conjugate acids using a continuum solvation model called the self-consistent isodensity polarizable continuum model (SCIPCM). The solvation energies were computed at the restricted Hartree-Fock (RHF) and second-order Møller-Plesset (MP2) levels of theory, as well as with the Becke3-Lee-Yang-Parr (B3LYP) density functional theory, using the standard 6-31G** Gaussian basis set. The RHF solvation energies are similar to those computed at the correlated MP2 and B3LYP theoretical levels. A model for computing protonation enthalpies for neutral bases in fluorosulfonic acid solvent leads to the equation ΔH_{prot, HSO3F}(B) = - PA(B) + ΔE_t(BH⁺) - ΔE_t(B) + β, where PA(B) is the gas phase proton affinity for base B, ΔE_t(BH⁺) is the SCIPCM solvation energy for the conjugate acid, and ΔE_t(B) is the solvation energy for the base. A fit to experimental values of ΔH_{prot, HSO3F}(B) for 10 neutral bases (H₂O, MeOH, Me₂O, H₂S, MeSH, Me₂S, NH₃, MeNH₂, Me₂NH, and PH₃) gives β = 238.4 ± 2.9 kcal/mol when ΔΔE_t is computed using the 0.0004 e · bohr^-3 isodensity surface for defining the solute cavity at the RHF/6-31G** level. The model predicts that for carbon monoxide ΔH_{prot, HSO3F}(CO) = 10 kcal/mol. Thus, protonation of CO is endothermic, and the conjugate acid HCO⁺ (formyl cation) behaves as a strong acid in fluorosulfonic acid.