Theoretical study of the red‐ and blue‐shifted hydrogen bonds of nitroxyl and acetylene dimers

Abstract

AbstractAb initio molecular orbital and density functional theory (DFT) in conjunction with different basis sets calculations were performed to study the CH…O red‐shifted and NH…π blue‐shifted hydrogen bonds in HNOC2H2 dimers. The geometric structures, vibrational frequencies and interaction energies were calculated by both standard and counterpoise (CP)‐corrected methods. In addition, the G3B3 method was employed to calculate the interaction energies. The topological and natural bond orbital (NBO) analysis were investigated the origin of NH…π blue‐shifted hydrogen bond. From the NBO analysis, the electron density decrease in the σ* (NH) is due to the significant electron density redistribution effect. The blue shifts of the NH stretching frequency are attributed to a cooperative effect between the rehybridization and electron density redistribution. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2006