ML4^2-几何和电子结构的理论研究(M=Ni^2＋，Pd^2＋，Pt^2＋；L=CN^-，Cl^-)  

Theoretical study of geometries and electronic structures of ML_4^(2-) (M=Ni^(2+),Pd^(2+),Pt^(2+) and L=CN^-,Cl^-)

作　　者：陈玉[1] 赵亮[1] 崔佳[1] 张福丽[1] 陈燕[1] 徐春明[1] 刘植昌[1] 

机构地区：[1]中国石油大学化学科学与工程学院,重质油国家重点实验室,北京102249

出　　处：《分子科学学报》2008年第6期381-386,共6页Journal of Molecular Science

基　　金：国家自然科学基金资助项目(20576078,20873180);国家杰出青年科学基金资助项目(20525621);重质油国家重点实验室开放课题;国家重点实验室自主课题资助项目

摘　　要：对具有16电子的镍族二价阴离子系列的几何和电子结构进行了研究.在从头算和密度泛函(DFT)的水平上计算得到的几何结构与实验结果具有较好的可比性.SVWN,BP86和B3LYP计算的键长、键角一般具有相同的趋势,但SVWN计算的键长有时偏短.MP2个别情况下表现出异于DFT的趋势.电荷分布计算结果表明:在高自旋态的(扭曲)四面体NiCl42-中,Ni具有较高的正电荷,MP2的计算值甚至接近两个正电荷;相对而言,低自旋态的平方四边形中金属原子拥有明显较低的正电荷.计算结果证明了传统观点,即Cl-是比CN-更弱的电子受体,这点在NiCl42-的情形下体现得特别明显,Cl-几乎没有为Ni2+提供电子或负电荷.The geometries and electronic structures of the tide anions are studied at several density functional theory （DFT）levels,such as SVWN, BP86 and B3LYP, and ab initio （MP2） levels. Calculated geometries axe generally comparable with experimental data.Same trends are obtained at these DFT levels, and MP2 has sometimes slightly different behaviors. All metal atoms of planar square structures possess significant low positive charges in the low spin states according to theoretical results. In comparison, Ni of distorted tetrahedron NiCL4^2- is showed to have a very high positive charge in the high spin state, - 2 e is calculated at the MP2 level. Therefore it is very obvious in the case of NiCl4^2- that Cl^- is a very weak electron donator. In another word, Cl^- has almost given neither electron nor negative charge to Ni^2＋ .

关 键 词：密度泛函(DFT) 从头算 四面体结构 平方平面结构 

分 类 号：O641[理学—物理化学]