Laboratorio de Quimica Teorica y Experimental-QuiTEx, Departamento de Quimica, Facultad Regional Resistencia, Universidad Tecnologica Nacional, French 414 (3500) Resistencia (Chaco), Argentina.
J Phys Chem A. 2010 Jan 14;114(1):552-62. doi: 10.1021/jp907550k.
Density functional theory (DFT) and atoms in molecules theory (AIM) were used to study the characteristic of the noncovalent interactions in complexes formed between Lewis bases (NH(3), H(2)O, and H(2)S) and Lewis acids (ClF, BrF, IF, BrCl, ICl, and IBr). In order to compare halogen and hydrogen bonds interactions, this study included hydrogen complexes formed by some Lewis bases and HF, HCl, and HBr Lewis acids. Ab initio, wave functions were generated at B3LYP/6-311++G(d,p) level with optimized structures at the same level. Criteria based on a topological analysis of the electron density were used in order to characterize the nature of halogen interactions in Lewis complexes. The main purpose of the present work is to provide an answer to the following questions: (a) why can electronegative atoms such as halogens act as bridges between two other electronegative atoms? Can a study based on the electron charge density answer this question? Considering this, we had performed a profound study of halogen complexes in the framework of the AIM theory. A good correlation between the density at the intermolecular bond critical point and the energy interaction was found. We had also explored the concentration and depletion of the charge density, displayed by the Laplacian topology, in the interaction zone and in the X-Y halogen donor bond. From the atomic properties, it was generally observed that the two halogen atoms gain electron population in response to its own intrinsic nature. Because of this fact, both atoms are energetically stabilized.
密度泛函理论（DFT）和分子中的原子理论（AIM）被用于研究路易斯碱（NH3、H2O 和 H2S）与路易斯酸（ClF、BrF、IF、BrCl、ICl 和 IBr）形成的配合物中非共价相互作用的特征。为了比较卤素键和氢键相互作用，本研究包括一些路易斯碱与 HF、HCl 和 HBr 路易斯酸形成的氢键配合物。在 B3LYP/6-311++G(d,p)水平上生成了从头算波函数，并用相同水平优化了结构。基于电子密度拓扑分析的标准被用于表征路易斯配合物中卤素相互作用的性质。本工作的主要目的是回答以下问题：（a）为什么电负性原子（如卤素）可以充当两个其他电负性原子之间的桥梁？基于电子电荷密度的研究可以回答这个问题吗？考虑到这一点，我们在 AIM 理论框架内对卤素配合物进行了深入研究。在分子间键临界点处的密度与能量相互作用之间发现了很好的相关性。我们还探索了在相互作用区和 X-Y 卤素供体键中，拉普拉斯拓扑显示的电荷密度的集中和耗尽。从原子性质来看，通常观察到两个卤素原子会根据其自身的固有性质获得电子。由于这个事实，两个原子都在能量上得到稳定。
