d→d Spectrum and High-Spin/Low-Spin Competition in d↑(6) Octahedral Coordination Compounds: ab Initio Study of Potential Energy Curves

Hé1ène Bolvin

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d→d Spectrum and High-Spin/Low-Spin Competition in d↑(6) Octahedral Coordination Compounds: ab Initio Study of Potential Energy Curves

机译：d↑（6）八面体配位化合物中的d→d光谱和高自旋/低自旋竞争：从头开始研究势能曲线

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Ab initio calculations were performed, using the CASPT2 method and moderate-size basis sets, on several d6 octahedral coordination compounds, Fe(CN)↓(6)↑(4-), Fe(NCH)↓(6)↑(2+), cis- and trans-Fe(CN)↓(2)(NCH)↓(4), and Cr(CO)↓(6). The study concentrates on the six lowest states of the d → d spectrum (three singlets, one quintet, and two triplets states), and on the dependence of their energy on the metal-ligand equilibrium distance. It has been exended to a d5 compound, Fe(CN)↓(6)↑(-3). The spin multiplicity of the ground states is correctly reproduced, and the metal-ligand distances and the vertical transitions energies, and dissociation energies are in good agreement with experiment. From the potential energy curves, it is possible to extract Racah＇s parameters, B and C, and the crystal field parameter △ as a function of the metal-ligand distance. The dependence of △on this distance is rationalized in terms of ligand field theory. Finally, the role of the triplet states in the spin transition is discussed.

机译：使用CASPT2方法和中等大小的基集对几种d6八面体配位化合物Fe（CN）↓（6）↑（4-），Fe（NCH）↓（6）↑（2+）进行从头计算），顺式和反式Fe（CN）↓（2）（NCH）↓（4）和Cr（CO）↓（6）。该研究集中于d→d光谱的六个最低状态（三个单重态，一个五重态和两个三重态），以及它们的能量对金属-配体平衡距离的依赖性。它已被扩展为d5化合物Fe（CN）↓（6）↑（-3）。正确地再现了基态的自旋多重性，并且金属-配体距离和垂直跃迁能以及解离能与实验很好地吻合。从势能曲线中，可以提取拉卡参数B和C以及晶场参数△随金属-配体距离的变化。根据配体场论合理化了△对该距离的依赖性。最后，讨论了三重态在自旋跃迁中的作用。

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《The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory》 |1998年第40期|共10页
作者
Hé1ène Bolvin;
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中图分类物理化学（理论化学）、化学物理学;
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8. Ab Initio Determination of the Ground State Potential Energy Curve for Ar2. [R] . Krauss, M., Stevens, W. J. 1982

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d→d Spectrum and High-Spin/Low-Spin Competition in d↑(6) Octahedral Coordination Compounds: ab Initio Study of Potential Energy Curves

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