For a series of phenol derivatives, the pKa of each is computed using an isodesmic reaction with phenol as the reference acid. Isodesmic reactions conserve bond number and bond type. Optimum equilibrium geometries, harmonic vibrational frequencies, and the corresponding Gibbs free energies are computed for all of the reactants and products in each isodesmic equation using density functional theory. The DFT functionals employed include wB97XD, and M06-2X. The basis sets employed are Dunning and coworkers' correlation consistent basis sets, aug-cc-pVDZ and aug-cc-pVTZ. The solvation model used is the continuous surface charge formalism for the polarizable continuum model (PCM). The solvents considered are water and DMSO. Results are presented for the ortho, meta, and para isomers of both amino and nitro derivatives. We gratefully acknowledge support from the NSF (EPS-0903787) and the W.M. Keck Foundation.

Computing relative acidities of phenol derivatives in DMSO and water with isodesmic equations

245th National Meeting (2013)

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