Zhang Yang, Wu Xun, Su Peifeng, Wu Wei
The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, iChEM, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, People's Republic of China.
J Phys Condens Matter. 2022 May 16;34(29). doi: 10.1088/1361-648X/ac6bd9.
In this paper, the nature of electron-pair bonds is explored from an energy decomposition perspective. The recently developed valence bond energy decomposition analysis (VB-EDA) scheme is extended for the classification of electron-pair bonds, which divides the bond dissociation energy into frozen, reference state switch, quasi-resonance and polarization terms. VB-EDA investigations are devoted to a series of electron-pair bonds, including the covalent bonds (H-H, HC-CH, HC-H, and HN-NH), the ionic bonds (Na-Cl, Li-F), the charge-shift (CS) bonds (HO-OH, F-F, Cl-Cl, Br-Br, H-F, F-Cl, HSi-F and HSi-Cl), and the inverted central carbon-carbon bond in [1.1.1] propallene. It is shown that the VB-EDA approach at the VBSCF level is capable of predicting the characters of the electron-pair bonds. The perspective from VB-EDA illustrates that a relatively high value of quasi-resonance term indicates a CS bond while a large portion of polarization term suggests a classical covalent bond.
本文从能量分解的角度探讨了电子对键的本质。最近开发的价键能量分解分析（VB-EDA）方案被扩展用于电子对键的分类，该方案将键解离能分为冻结项、参考态转换项、准共振项和极化项。VB-EDA研究致力于一系列电子对键，包括共价键（H-H、HC-CH、HC-H和HN-NH）、离子键（Na-Cl、Li-F）、电荷转移（CS）键（HO-OH、F-F、Cl-Cl、Br-Br、H-F、F-Cl、HSi-F和HSi-Cl）以及[1.1.1]丙二烯中中心碳-碳反向键。结果表明，VBSCF水平的VB-EDA方法能够预测电子对键的特征。VB-EDA的观点表明，准共振项的相对较高值表明是CS键，而极化项的很大一部分表明是经典共价键。
