Du Jiguang, Sun Xiyuan, Jiang Gang
College of Physical Science and Technology, Sichuan University, Chengdu 610064, China.
College of Sciences, Sichuan Agricultural University, Ya'an 625014, China.
Int J Mol Sci. 2016 Apr 11;17(4):414. doi: 10.3390/ijms17040414.
The interaction natures between Pu and different ligands in several plutonyl (VI) complexes are investigated by performing topological analyses of electron density. The geometrical structures in both gaseous and aqueous phases are obtained with B3LYP functional, and are generally in agreement with available theoretical and experimental results when combined with all-electron segmented all-electron relativistic contracted (SARC) basis set. The Pu- O y l bond orders show significant linear dependence on bond length and the charge of oxygen atoms in plutonyl moiety. The closed-shell interactions were identified for Pu-Ligand bonds in most complexes with quantum theory of atoms in molecules (QTAIM) analyses. Meanwhile, we found that some Pu-Ligand bonds, like Pu-OH(-), show weak covalent. The interactive nature of Pu-ligand bonds were revealed based on the interaction quantum atom (IQA) energy decomposition approach, and our results indicate that all Pu-Ligand interactions is dominated by the electrostatic attraction interaction as expected. Meanwhile it is also important to note that the quantum mechanical exchange-correlation contributions can not be ignored. By means of the non-covalent interaction (NCI) approach it has been found that some weak and repulsion interactions existed in plutonyl(VI) complexes, which can not be distinguished by QTAIM, can be successfully identified.
通过对电子密度进行拓扑分析，研究了几种钚酰（VI）配合物中钚与不同配体之间的相互作用性质。使用B3LYP泛函获得了气相和水相中的几何结构，当与全电子分段全电子相对论收缩（SARC）基组结合时，这些结构总体上与现有的理论和实验结果一致。钚-氧酰键级对键长和钚酰部分中氧原子的电荷表现出显著的线性依赖性。通过分子中原子的量子理论（QTAIM）分析，在大多数配合物中确定了钚-配体键的闭壳层相互作用。同时，我们发现一些钚-配体键，如Pu-OH(-)，表现出弱共价性。基于相互作用量子原子（IQA）能量分解方法揭示了钚-配体键的相互作用性质，我们的结果表明，所有钚-配体相互作用如预期的那样以静电吸引相互作用为主导。同时还需要注意的是，量子力学交换相关贡献不能被忽略。通过非共价相互作用（NCI）方法发现，在钚酰（VI）配合物中存在一些无法被QTAIM区分的弱相互作用和排斥相互作用，可以成功地识别出来。
