Density functional study of first row transition metal dihalides
Density functional study of first row transition metal dihalides
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第一行过渡金属二卤化物的密度泛函研究
DOI：
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发表时间：
1998
期刊：
影响因子：
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通讯作者：
W. Schwarz
中科院分区：
文献类型：
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作者：
S. Wang;W. Schwarz
与之前的配体场预测相反，金属 3d 轨道的标准能量顺序 δ<π<σ，此处未重现。自始至终，由于这些线性双配位化合物中 σ 供体诱导的 3d-4s 杂交，3dσ 分子轨道 (MO) 水平相当低，而 3dπ 则相当高，因为在二方卤化物的短距离处，卤素配体具有明显的 π 供体特征。这导致了基态的意外电子分布和不寻常的电子态顺序。计算结果总体上与最近的实验结果一致。该方法产生半定量正确的几何参数和振动频率，以及定性正确的解离能趋势。这些性质显示出二次周期性，类似于八面体高自旋配合物的二次周期性，尽管出于不同的电子原因。未知结构、振动频率和解离能...
In contrast to former ligand field predictions, the standard energetic order of the metal 3d orbitals, δ<π<σ, is not reproduced here. Throughout, the 3dσ molecular orbital (MO) level is found rather low lying because of σ-donating ligand induced 3d-4s hybridization in these linear dicoordinated compounds, while the 3dπ is rather high due to the pronounced π-donor character of the halogen ligands at the short distances of the digonal halides. This results in an unexpected electron distribution for the ground state and in an unusual order of electronic states. The calculations are in general consistent with recent experimental findings. The approach yields semiquantitatively correct geometric parameters and vibrational frequencies, and qualitatively correct trends for the dissociation energies. Those properties show a secondary periodicity, similar to the one known for octahedral high-spin complexes, though for different electronic reasons. Unknown structures, vibrational frequencies, and dissociation energ...