Computational Study on Mössbauer Isomer Shifts of Some Organic-neptunium (IV) Complexes
Computational Study on Mössbauer Isomer Shifts of Some Organic-neptunium (IV) Complexes
复制标题
一些有机镎（IV）配合物穆斯堡尔异构体位移的计算研究
DOI：
10.5562/cca2746
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发表时间：
2015
影响因子：
0.3
通讯作者：
S. Nakashima
中科院分区：
文献类型：
--
作者：
M. Kaneko;S. Miyashita;S. Nakashima
本文用相对论密度泛函理论计算了几种有机镎（IV）配合物Cp_3NpIVX（Cp = η_5-C_5H_5; X = BH_4，Cl，OtBu，Ph，nBu）的成键性质.我们采用标量相对论ZORA哈密顿量与全电子基组（SARC）。用B2 PLYP/ SARC理论计算得到的配合物中Np核位置的电子密度与237 Np体系的穆斯堡尔谱实验结果有很强的相关性。键重叠布居分析结果表明，键强度按X = BH_4、Cl、OtBu、Ph、nBu的顺序递减。这种趋势取决于Np 5 f电子与X配体之间的共价相互作用的程度。计算结果表明，估算5 f轨道的成键贡献对于理解有机锕系元素配合物的电子态是非常重要的。
Relativistic DFT calculations are applied to some organo-neptunium (IV) complexes, Cp3NpIVX (Cp = η5-C5H5; X = BH4, Cl, OtBu, Ph, nBu), in order to understand their bonding properties between Np and the ligands. We employ scalar-relativistic ZORA Hamiltonian with all-electron basis set (SARC). The calculated electron densities at Np nucleus position in the complexes at B2PLYP / SARC theory strongly correlate to the experimental Mössbauer isomer shifts of 237Np system. The result of bond overlap population analysis indicates that the bonding strength decreases in order of X = BH4, Cl, OtBu, Ph and nBu. The tendency depends on the degree of the covalent interaction between Np 5f-electron and X ligand. It is suggested that it is important to estimate the bonding contribution of 5f-orbital to understand the electronic state for organoactinide complexes.