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关于涉及三重态二苯基卡宾的非共价相互作用的理论研究

Theoretical study on the noncovalent interactions involving triplet diphenylcarbene.

作者信息

Zhao Chunhong, Lin Hui, Shan Aiting, Guo Shaofu, Li Xiaoyan, Zhang Xueying

机构信息

Huihua College of Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.

College of Chemistry and Materials Science, Hebei Key Laboratory of Inorganic Nano-materials, Hebei Normal University, Shijiazhuang, 050024, People's Republic of China.

出版信息

J Mol Model. 2021 Jul 9;27(8):224. doi: 10.1007/s00894-021-04838-6.

Abstract

The properties of some types of noncovalent interactions formed by triplet diphenylcarbene (DPC) have been investigated by means of density functional theory (DFT) calculations and quantum theory of atoms in molecule (QTAIM) studies. The DPC···LA (LA = AlF, SiF, PF, SF, ClF) complexes have been analyzed from their equilibrium geometries, binding energies, and properties of electron density. The triel bond in the DPC···AlF complex exhibits a partially covalent nature, with the binding energy - 65.7 kJ/mol. The tetrel bond, pnicogen bond, chalcogen bond, and halogen bond in the DPC···LA (LA = SiF, PF, SF, ClF) complexes show the character of a weak closed-shell noncovalent interaction. Polarization plays an important role in the formation of the studied complexes. The strength of intermolecular interaction decreases in the order LA = AlF > ClF > SF > SiF > PF. The electron spin density transfers from the radical DPC to ClF and SF in the formation of halogen bond and chalcogen bond, but for the DPC···AlF/SiF/PF complexes, the transfer of electron spin density is minimal.

摘要

通过密度泛函理论(DFT)计算和分子中原子的量子理论(QTAIM)研究,对三重态二苯基卡宾(DPC)形成的某些类型非共价相互作用的性质进行了研究。从平衡几何结构、结合能和电子密度性质等方面对DPC···LA(LA = AlF、SiF、PF、SF、ClF)配合物进行了分析。DPC···AlF配合物中的三族元素键表现出部分共价性质,结合能为 - 65.7 kJ/mol。DPC···LA(LA = SiF、PF、SF、ClF)配合物中的四族元素键、氮族元素键、氧族元素键和卤键表现出弱闭壳层非共价相互作用的特征。极化在所研究配合物的形成中起重要作用。分子间相互作用强度按LA = AlF > ClF > SF > SiF > PF的顺序降低。在卤键和氧族元素键形成过程中,电子自旋密度从自由基DPC转移到ClF和SF,但对于DPC···AlF/SiF/PF配合物,电子自旋密度的转移极小。

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