We report thermodynamic, geometric, and electronic parameters for the interaction between neutral ligands and the [Hg(H₂O)]²⁺ dication, using the B3LYP/6–311 + G(d,p) approach. Gibbs free energies for the interaction were employed to rank the affinity order of the several neutral ligands. To identify the parameters that characterize the affinity between the two fragments, the metal-ligand interaction was analyzed according to the EDA, NBO, and QTAIM decomposition schemes. The phosphine oxide showed the highest affinity for the Hg(H₂O)²⁺ dication, mainly due to the P=O bond polarization. Ligands containing the sulfur atom, characterized by a high covalent component for the metal-ligand interaction, are the following in the interaction order. According to the Gibbs free energy for substitution of one water molecule in the [Hg(H₂O)₂]²⁺ complex, the sequence for the affinity order is: phosphine oxide > thioketone > thioesther > lactam > amide > amine > carboxylic acid > thiophene > ketone > esther > thiol > thiocyanate > ammonia > disulfide > aldehyde > ether > haloydrin > alcohol > enol > azide.

SynopsisThe interaction between the Hg²⁺ cation and monodentate ligands containing S, O, or N atoms was evaluated in terms of energetic (bond strength, electrostatic and covalent interactions, donation energy), geometric (metal-ligand distance), electronic (atomic charges, orbital overlap, orbital hybridization) and topologic parameters.

中文翻译：

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使用NBO，EDA和QTAIM对Hg2 +和单齿中性配体之间的相互作用进行DFT分析。

我们使用B3LYP / 6–311 + G（d，p）方法报告中性配体与[Hg（H ₂ O）] ²⁺指示剂之间相互作用的热力学，几何和电子参数。相互作用的吉布斯自由能被用来排列几个中性配体的亲和力顺序。为了确定表征两个片段之间亲和力的参数，根据EDA，NBO和QTAIM分解方案分析了金属-配体相互作用。氧化膦对Hg（H ₂ O）^2+的亲和力最高指示，主要是由于P = O键极化。包含硫原子的配体，其特征在于用于金属-配体相互作用的高共价组分，按相互作用顺序如下。根据[Hg（H ₂ O）₂ ] ²⁺络合物中一个水分子取代的吉布斯自由能，亲和力顺序为：氧化膦>硫酮>硫醚>内酰胺>酰胺>胺>羧酸>噻吩>酮>醚>硫醇>硫氰酸盐>氨>二硫化物>醛>醚>卤化物>醇>烯醇>叠氮化物

概要根据能量（键强度，静电和共价相互作用，捐赠能），几何（金属-配体距离），电子（原子电荷）评估了Hg ²⁺阳离子与含有S，O或N原子的单齿配体之间的相互作用，轨道重叠，轨道杂交）和拓扑参数。