| M(CO)4~(2+)(M=Ni,Pd,Pt)的几何结构与自旋态的理论研究 |
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| 引用本文： | 赵亮,张福丽,陈燕,陈玉.M(CO)4~(2+)(M=Ni,Pd,Pt)的几何结构与自旋态的理论研究[J].分子科学学报,2009,25(6). |
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| 作者姓名： | 赵亮 张福丽 陈燕 陈玉 |
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| 作者单位： | 中国石油大学重质油国家重点实验室,化学科学与工程学院,北京,102249 |
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| 基金项目： | 国家自然科学基金资助项目，国家重点实验室自主课题资助项目，重质油国家重点实验室开放课题资助项目 |
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| 摘 要： | 对标题化合物的几何结构和可能的自旋态在密度泛函DFT-BP86和从头算的水平上进行了研究.计算结果表明:作为16电子配合物阳离子,Pd(CO)_4~(2+)和Pt(CO)~(2+)都以低自旋态平面四边形构型存在,这与实验事实相符,计算得到的键长Pd-C和Pt-C相对趋势也与实验数据一致.而对于Ni(CO)_4~(2+)阳离子计算,在低自旋态平面四边形构型和高自旋态的(扭曲)四面体之间无法给出明确的答案,因为CCSD(T)//BP86和CCSD(T)//MP2水平下得到的两种结构之间的能量差几乎可以忽略.
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| 关 键 词： | 密度泛函(DFT) 四面体结构 平面四边形结构 自旋态 |
Geometries and spin state of tetracarbonyl metal cations of Ni group M(CO)4~(2+)(M=Ni,Pd,Pt):a theoretical study |
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| ZHAO Liang,ZHANG Fu-li,CHEN Yan,CHEN Yu.Geometries and spin state of tetracarbonyl metal cations of Ni group M(CO)4~(2+)(M=Ni,Pd,Pt):a theoretical study[J].Journal of Molecular Science,2009,25(6). |
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| Authors: | ZHAO Liang ZHANG Fu-li CHEN Yan CHEN Yu |
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| Institution: | ZHAO Liang,ZHANG Fu-li,CHEN Yan,CHEN Yu(State Key Laboratory of Heavy Oil,Chemistry and Chemical Engineering College,China University of Petroleum,Beijing 102249,China) |
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| Abstract: | The geometries and spin states of the title cations are studied at the density functional theory (DFT-BP86) and ab initio levels.Calculated geometries of M(CO)_4~(2+)(M=Pd,Pt) are comparable with experimental data.Both are calculated to be in planar square structures and the experimental bond length order Pd-C> Pt-C is also reproduced by the theoretical calculations.As to Ni(CO)_4~(2+),a definitely sure answer can not be given:which one is preferred between (distorted) tetrahedron and planar square structure? The relative energies between these two configurations at the CCSD(T)//BP86 and CCSD(T)//MP2 levels are both negligible. |
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| Keywords: | density functional theory (DFT) ab initio tetrahedron planar square structure spin state |
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