Hydrogen Bonding Interaction of Formic Acid-, Formaldehyde-, Formylfluoride-Nitrosyl Hydride: Theoretical Study on the Geometries, Interaction Energies and Blue-or Red-Shifted Hydrogen Bonds

摘要

The hydrogen bonding interaction of formic acid-, formaldehyde-, formylfluoride-nitrosyl hydride complexes was investigated by the density functional theory (DFT) and ab inito method in conjunction with 6-311++G(2d,2p)basis set. The geometries, vibrational frequencies and interaction energies of the complexes were calculated by both standard and CP-corrected methods respectively. Moreover, G3B3 method was employed to estimate the interaction energies. There are C-H…O, N-H…O, N-H…F blue-shifted H-bonds and red-shifted O-H…O H-bond in the complexes. Electron density redistribution and rehybridization contribute to the N-H and C-H blue shifts. All geometric reorganizations contribute to the N-H blue shifts and partial geometric reorganizations contribute to the C-H blue shifts. The geometric reorganizations of the complex C except ∠H(5)-O(4)-C(1) contribute to the O-H red shift. For the N-H blue shifts, the effect of r(N-O) variation on the N-H blue shifts is larger than that of ∠H-N-O variation. Rehybridization plays a dominant role in the degree of N-H blue shifts, whereas the electron density redistribution contributes more to the degree of C-H blue shifts than the other effects do.