Electron density and energy decomposition analysis in hydrogen-bonded complexes of azabenzenes with water, acetamide, and thioacetamide

Abstract

Ab initio and density functional theoretical studies on hydrogen-bonded complexes of azabenzenes with water, acetamide, and thioacetamide have been carried out to explore the controversy involved in the relative order of their stability in a systematic way. The interaction energies of these complexes have been analyzed using the Morokuma energy decomposition method, and the nature of the various hydrogen bonds formed has been investigated through topological aspects using Bader's atom in a molecule (AIM) theory. Morokuma energy decomposition analysis reveals that the major contributions to the energetics are from the polarization (PL) and charge transfer (CT) energies. From the calculated topological results, excellent linear correlation is shown to exist between the hydrogen-bond length, electron density [ρ (r)], and its Laplacian [∇²ρ (r)] at the bond critical points for all the complexes considered.