Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U)
Low-lying electronic states of lanthanocenes and actinocenes M(C8H8)2 (M=Nd, Tb, Yb, U)
复制标题
镧茂和放线茂的低电子态 M(C8H8)2 (M=Nd, Tb, Yb, U)
DOI：
10.1063/1.474698
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发表时间：
1997
影响因子：
4.4
通讯作者：
P. Fulde
中科院分区：
文献类型：
--
作者：
Wenjian Liu;M. Dolg;P. Fulde
采用大尺度态平均多组态自洽场、多参考组态相互作用和平均耦合对泛函计算方法，对双π-环辛四烯（或双[8]轮烯）金属夹心配合物M（C_8H_8）_2（M=Nd，Tb，Yb，U）的基态和激发态进行了计算，并利用能量一致的准相对论赝势计算了相对论效应.发现镧系茂的基态构型为4fnπ3，而锕系茂的基态构型为5 fn −1π4。较轻和较重的镧系茂的基态分别是较低和较高的多重态，这是由中心金属4fn亚壳层的最高自旋多重数与未配对配体π电子之间的耦合产生的，而它们总是具有最高可能的多重数5 fn −1π4。金属环的距离和对称的金属环的伸缩频率的报告。特色是……
Large-scale state-averaged multiconfiguration self-consistent field, multireference configuration interaction, and averaged coupled-pair functional calculations, including relativistic effects by means of energy-consistent quasirelativistic pseudopotentials, have been carried out for the ground and low-lying excited states of the di-π-cyclooctatetraene (or bis[8]annulene) metal sandwich complexes M(C8H8)2 (M=Nd, Tb, Yb, U). It is found that the ground state configurations for the lanthanocenes are 4fnπ3, while for the actinocenes they are 5fn−1π4. The ground states for the lighter and heavier lanthanocenes are, respectively, the lower and higher multiplicity states resulting from the coupling between the highest possible spin–multiplicity of the central metal 4fn subshell and the unpaired ligand π electron, whereas they always have the highest possible multiplicity of 5fn−1π4 for the actinocenes. The metal–ring distances and symmetric metal–ring stretching frequencies are reported. The special characteris...