The single-electron hydrogen bond: The interaction between the CH3 radical and HCNO and HNCO

Abstract

All calculations were carried out using the UB3LYP method with the 6-311++G(2d,2p) and aug-cc-pVTZ basis sets. The methyl radical (CH₃) complexes H₃C....HCNO and H₃C....HNCO are reported to show the existence of a single-electron hydrogen bond. The C3v symmetry is obtained for the H₃C ....HCNO complex and the H₃C....HNCO complex has the Cs symmetry. To better understand the intermolecular H-bond interactions, NBO analysis and topological analysis of electron density at bond critical points (BCPs) using Bader's atoms-in-molecules theory were performed. The interaction energies of the H₃C....HCNO and H₃C....HNCO complexes arc in turn -0.329 kcal.mol^-1 and -0.525 kcat. mol^-1 at the UB3LYP/ aug-cc-pVTZ level with the ZPE and BSSE corrections, respectively. The red shifts have obtained in both the examined complexes