Theoretical studies on tautomerism of imidazole-2-selenone

Abstract

The tautomerism of all possible forms of imidazole selenone (ISe1–ISe6), induced by proton transfer was studied theoretically in different environments including gas phase, continuum solvent, and microhydrated environment with one explicit water molecule. The calculations were performed at the MP2 and CAM-B3LYP levels of theory, separately. It was found that the imidazole selenone, in the form of ISe3, is the most stable isomer in both gas phase and solvent. The activation energy for conversion of ISe3 to imidazole selenol (ISe6), as the second stable form, is 41.72 and 43.0 kcal/mol in the gas phase and water, respectively. The infrared spectral frequencies as well as the vibrational frequency shifts were reported and assigned to their corresponding vibrational modes. In addition, the variation of dipole moments and charges on the atoms with change of solvent was studied. The energies of HOMO, LUMO, and HOMO–LUMO gap were calculated in both gas phase and solvent. Specific solvent effects with addition of water molecule near the electrophilic centers of tautomers and the transition states of proton transfer, assisted by water molecule, were investigated. It was found that the water molecule can form different hydrogen bonds with the molecule. Aggregation of the isomers with water molecule does not change the order of stability of isomers, but proton transfer reaction assisted by a water molecule needs less energy than when the proton shifts through the intramolecular process.