NBO电荷计算对电中性原理的检验  

Verifying Principle of Electroneutrality by NBO Charge Calculations

作　　者：徐嘉伟 邓力克 张浩哲 张焕禹 罗羽晨 颜馨雅 包建春[1] 方敏[1,2,3] 吴勇[1] XU Jia-Wei;DENG Li-Ke;ZHANG Hao-Zhe;ZHANG Huan-Yu;LUO Yu-Chen;YAN Xin-Ya;Bao Jian-Chun;FANG Min;WU Yong(Jiangsu Key Laboratory of New Power Batteries,Jiangsu Collaborative Innovation Center of Biomedical Functional Materials,School of Chemistry and Materials Science,Nanjing Normal University,Nanjing 210023,China;Jiangsu Key Laboratory for Numerical Simulation of Large Scale Complex Systems(NSLSCS),Nanjing Normal University,Nanjing 210023,China;State Key Laboratory of Coordination Chemistry,Nanjing University,Nanjing 210023,China)

机构地区：[1]南京师范大学化学与材料科学学院,江苏省生物功能材料协同创新中心,江苏省新型动力电池重点实验室,南京210023 [2]南京师范大学,江苏省大规模复杂系统数值模拟重点实验室,南京210023 [3]南京大学,配位化学国家重点实验室,南京210023

出　　处：《无机化学学报》2020年第11期2157-2168,共12页Chinese Journal of Inorganic Chemistry

基　　金：国家自然科学基金(No.21071082,21471081,21533012);江苏省大学生创新创业培训计划(No.201910319079Y)资助项目。

摘　　要：我们在B3LYP/6⁃31++G(d,p)计算级别下计算了[M(H2O)6]3+(M=Sc^Co)、[Co􀃮L6](L=F-、H2O、NH3、CN-),以及基于α⁃Al2O3晶体结构搭建的铝氧簇Al3O(OH)7(H2O)5(Al3)和Al6O6(OH)6(H2O)5(Al6)的NBO电荷。除[Co(NH3)6]3+外,其它化合物均不符合经典教科书中的电中性原理,具有超出-1^+1范围的电荷。此外,我们发现中心原子的电荷受到配位原子种类的极大影响,而这一规律未在电中性原理的表述中。计算结果表明,从[CoF6]3-到[Co(CN)6]3-,中心离子上所带电荷量从+1.639变化至-1.360,且中心离子上所带电荷随其离子势的增大而降低。另外基于对铝氧簇的计算,我们预测α⁃Al2O3中的Al原子所带电荷应为2.1±0.1。NBO charges of [M(H2 O)6]3+(M=Sc^Co),[Co(Ⅲ)L6](L=F-,H2O,NH3,CN-),Al3O(OH)7(H2O)5(Al3) and Al6O6(OH)6(H2O)5(Al6) created based on α-Al2O3 were calculated at B3 LYP/6-31++G(d,p) level of density functional theory(DFT).Except for [Co(NH3)6]3+,they all violate the principle of electroneutrality(EN) by having charges outside the range of +1 to-1.In addition,the charge for the central metal ion is drastically influenced by the type of the coordination atoms,which is not included in the current EN principle.The charges of Co3+in [CoF6]3-and[Co(CN)6]3- were found to be 1.639 and-1.360,respectively.When the ionic potential of the central atom increases,its charge would decrease.Based on our calculation,we predict the charge of Al in α-Al2 O3 is 2.1±0.1.

关 键 词：电中性原理 理论与计算化学 NBO电荷 密度泛函理论 

分 类 号：O641.12[理学—物理化学]