Faculty of Chemistry, University of the Basque Country UPV/EHU,and Donostia International Physics Center (DIPC), P.K. 1072, 20080, Donostia, Euskadi, Spain,
J Mol Model. 2013 Nov;19(11):4713-21. doi: 10.1007/s00894-012-1463-7. Epub 2012 Jul 8.
MP2(full)/6-311++G(3df,3pd) calculations were carried out on complexes linked through various non-covalent Lewis acid - Lewis base interactions. These are: hydrogen bond, dihydrogen bond, hydride bond and halogen bond. The quantum theory of ´atoms in molecules´ (QTAIM) as well as the natural bond orbitals (NBO) method were applied to analyze properties of these interactions. It was found that for the A-H…B hydrogen bond as well as for the A-X…B halogen bond (X designates halogen) the complex formation leads to the increase of s-character in the A-atom hybrid orbital aimed toward the H or X atom. In opposite, for the A…H-B hydride bond, where the H-atom possesses negative charge, the decrease of s-character in the B-atom orbital is observed. All these changes connected with the redistribution of the electron charge being the effect of the complex formation are in line with Bent's rule. The numerous correlations between energetic, geometrical, NBO and QTAIM parameters were also found.
对通过各种非共价路易斯酸碱相互作用连接的配合物进行了 MP2(full)/6-311++G(3df,3pd) 计算。这些相互作用包括氢键、双氢键、氢化物键和卤素键。应用“分子中的原子量子理论”（QTAIM）和自然键轨道（NBO）方法来分析这些相互作用的性质。结果表明，对于 A-H…B 氢键以及 A-X…B 卤素键（X 表示卤素），配合物的形成导致 A 原子杂化轨道中指向 H 或 X 原子的 s 特征增加。相反，对于 A…H-B 氢化物键，其中 H 原子带负电荷，观察到 B 原子轨道中 s 特征的减少。所有这些与配合物形成相关的电子电荷重新分布有关的变化都符合本特规则。还发现了能量、几何形状、NBO 和 QTAIM 参数之间的大量相关性。
