【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[Co F₆]^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。更多还原

【Abstract】 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 A1 in α-Al₂ O₃ is 2.1±0.1.更多还原