Intermediate-Spin State of a 3d Ion in the Octahedral Environment and Generalization of the Tanabe鈥揝ugano Diagrams

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• 作者：Karina V. Lamonova ; Elena S. Zhitlukhina ; Roman Yu. Babkin ; Sergei M. Orel ; Sergei G. Ovchinnikov ; Yurii G. Pashkevich
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：November 24, 2011
• 年：2011
• 卷：115
• 期：46
• 页码：13596-13604
• 全文大小：1195K
• 年卷期：v.115,no.46(November 24, 2011)
• ISSN：1520-5215

文摘

Electronic spectra of 3d<sup>nsup> transition ions in an octahedral ligand surrounding have been studied using the modified crystal field approach (MCFA), which includes a relativistic spin鈥搊rbital interaction. A new variable parameter, the effective nuclear charge Z<sub>effsub> of a metal ion that allows accounting implicitly the covalence degree of a metal鈥搇igand bond, has been introduced. Energy diagrams similar to the Tanabe鈥揝ugano ones have been calculated. To study the spin state evolution of the metal ion in an arbitrary distorted octahedral complex, a spin state diagram approach has been proposed. The intermediate-spin (IS) state problem for 3d<sup>4sup>, 3d<sup>5sup>, and 3d<sup>6sup> metal ions has been considered and conditions for the IS state realization have been formulated. The regions of the mixed high-, intermediate-, and low-spin states have been found. The possibility of coexistence of the different spin states of 3d ions in the octahedral complexes has been considered using crystallography data for the YBaCo<sub>2sub>O<sub>5.5sub> layered cobaltite.