Ground and excited state intramolecular proton transfer in salicylic acid: an ab initio electronic structure investigation

Abstract

Energetics of the ground and excited state intramolecular proton transfer in salicylic acid have been studied by ab initio molecular orbital calculations using the 6-31G^∗∗ basis set at the restricted Hartree-Fock (RHF) and configuration interaction-single excitation (CIS) levels and also using the semiempirical method AM1 at the RHF level as well as with single and pair doubles excitation configuration interaction spanning eight frontier orbitals (PECI = 8). The ab initio potential energy profile for intramolecular proton transfer in the ground state reveals a single minimum corresponding to the primary form. In the first excited singlet state, however, there are two minima corresponding to the primary and tautomeric forms, separated by a barrier of ~6 kcal/mol, thus accounting for dual emission in salicylic acid. Electron density changes with electronic excitation and tautomerism indicate no zwitterion formation. Changes in spectral characteristics with change in pH, due to protonation and deprotonation of salicylic acid, are also accounted for, qualitatively. Although the AM1 calculations suggest a substantial barrier for proton transfer in the ground as well as the first excited state of SA, it predicts the transition wavelength in near quantitative accord with the experimental results for salicylic acid and its protonated and deprotonated forms.