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Theoretical study of bifurcated bent blue-shifted hydrogen bonds CH2···Y

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Abstract

Ab initio quantum chemistry methods were applied to study the bifurcated bent hydrogen bonds Y··· H2CZ (Z = O, S, Se) and Y···H2CZ2 (Z = F, Cl, Br) (Y = Cl−, Br−) at the MP2/6-311++G(d,p) and MP2/6-311++G(2df,2p) levels. The results show that in each complex there are two equivalent blue-shifted H-bonds Y···H-C, and that the interaction energies and blue shifts are large, the energy of each Y···H-C H-bond is 15–27 kJ/mol, and Δr(CH) = −0.1 − −0.5 pm and Δv(CH) = 30 − 80 cm−1. The natural bond orbital analysis shows that these blue-shifted H-bonds are caused by three factors: large rehybridization; small direct intermolecular hyperconjugation and larger indirect intermolecular hyperconjugation; large decrease of intramolecular hyperconjugation. The topological analysis of electron density shows that in each complex there are three intermolecular critical points: there is one bond critical point between the acceptor atom Y and each hydrogen, and there is a ring critical point inside the tetragon YHCH, so these interactions are exactly H-bonding.

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  1. School of Chemistry and Chemical Engineering, Southwest University, Chongqing, 400715, China

    AnYong Li

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Li, A. Theoretical study of bifurcated bent blue-shifted hydrogen bonds CH2···Y. Sci. China Ser. B-Chem. 51, 623–631 (2008). https://doi.org/10.1007/s11426-008-0064-x

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  • DOI: https://doi.org/10.1007/s11426-008-0064-x

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