Halogen Bonding and Other Iodine Interactions in Crystals of Dihydrothiazolo(oxazino)quinolinium Oligoiodides from the Electron-Density Viewpoint
Halogen Bonding and Other Iodine Interactions in Crystals of Dihydrothiazolo(oxazino)quinolinium Oligoiodides from the Electron-Density Viewpoint
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DOI：
10.1021/cg500958q
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发表时间：
2014-11-01
影响因子：
3.8
通讯作者：
Tsirelson, Vladimir G.
中科院分区：
文献类型：
--
作者：
Bartashevich, Ekaterina V.;Yushina, Irina D.;Tsirelson, Vladimir G.
基于三维周期性KohnSham方法，研究了含不同结构低碘负离子的二氢噻唑并（恶嗪）喹啉盐晶体中电子密度的空间组织.结合单电子势和静电势分析，发现晶体环境中碘原子的卤键（II型相互作用）和货车范德华（I型相互作用）之间存在显著差异。碘部分的零通量原子间表面上静电势中的s-孔痕迹是卤键的显着特征;它们不出现在弱范德瓦耳斯货车I中..我完全没有互动。的电子密度和静电势的梯度场的叠加的分析，允许检测的强电子沿沿着低聚碘链[I-3.我... I-3];通过碘分子I-2作为介体，电子密度从I-3部分移动到阳离子。实验测得的离解能D-e（I-I/I）与实验值之间存在定量关系。I）和键临界点的动能密度在整个范围内观察到的碘相互作用已经建立。
The spatial organization of electron density in dihydrothiazolo(oxazino)quinolinium crystals with oligoiodide anions of various structures has been studied on the basis of 3D periodic KohnSham calculations. The combination of QTAIMC and the analysis of one-electron potential and electrostatic potential has revealed the significant differences between halogen bonds (Type II interactions) and van der Waals (Type I) interactions for iodine atoms in crystalline environment. The traces of s-holes in electrostatic potential on the zero-flux interatomic surfaces of iodine moieties are the distinctive feature of halogen bonding; they do not appear in the weak van der Waals I...I interactions at all. The analysis of superposition of the gradient fields of the electron density and electrostatic potential has allowed detection of the strong electron redistribution along the oligoiodide chain [I-3...I-I...I-3]; the electron density is shifted from I-3 moiety to the cation via iodine molecule I-2 as a mediator. The quantitative relationship between the experimentally measured dissociation energy D-e(I-I/I...I) and the kinetic energy density at the bond critical point in the whole range of observed iodine interactions has been established.