Kimika Fakultatea, Euskal Herriko Unibertsitatea and Donostia International Physics Center (DIPC), Donostia, Euskadi, Spain.
J Phys Chem A. 2011 May 12;115(18):4765-73. doi: 10.1021/jp2005327. Epub 2011 Apr 14.
The MP2/6-311++G(d,p) calculations were performed on several hydrogen-bonded systems. Different complexes were taken into account to analyze various types of hydrogen bonds, possessing different types of proton donors and proton acceptors as well as characterized by the broad range of the interaction energy. The Quantum Theory of Atoms in Molecules is applied. The results of the hybrid variational-perturbational approach are discussed. The unique properties of hydrogen bonds, where π-electrons act as the proton acceptor (X-H···π), are analyzed, and these interactions are compared with the other types of hydrogen bonds, mainly with C-H···Y interactions. It is shown that for X-H···π systems the ellipticity at the bond critical point of the proton···acceptor interaction is much greater than for the other types of hydrogen bonds. However, both X-H···π and C-H···Y interactions are characterized by the dominance of the dispersive energy.
采用 MP2/6-311++G(d,p)方法对几个氢键体系进行了计算。考虑了不同的复合物，以分析具有不同质子供体和质子受体类型以及具有广泛相互作用能的各种氢键。应用了分子中的原子量子理论。讨论了混合变分微扰方法的结果。分析了π电子作为质子受体（X-H···π）的氢键的独特性质，并将这些相互作用与其他类型的氢键（主要是 C-H···Y 相互作用）进行了比较。结果表明，对于 X-H···π 体系，质子···受体相互作用的键临界点的椭圆率远大于其他类型的氢键。然而，X-H···π 和 C-H···Y 相互作用都以分散能为主导。
