Spin-Orbit Interactions in Osmium Complexes

I. P. Asanov; Асанов И. П.; A. D. Fedorenko; Федоренко А. Д.; D. B. Vasilchenko; Васильченко Д. Б.; M. A. Grebenkina; Гребенкина М. А.; A. N. Lavrov; Лавров А. Н.; I. V. Korol’kov; Корольков И. В.; V. V. Kriventsov; Кривенцов В. В.; S. V. Trubina; Трубина С. В.; T. I. Asanova; Асанова Т. И.

doi:10.31857/S1028096023060043

Spin-Orbit Interactions in Osmium Complexes

Authors: Asanov I.P.¹, Fedorenko A.D.¹, Vasilchenko D.B.¹, Grebenkina M.A.¹, Lavrov A.N.¹, Korol’kov I.V.¹, Kriventsov V.V.², Trubina S.V.¹, Asanova T.I.¹
Affiliations:
1. Nikolaev Institute of Inorganic Chemistry, Siberian Branch of RAS
2. Federal Research Center Boreskov Institute of Catalysis
Issue: No 6 (2023)
Pages: 3-14
Section: Articles
URL: https://rjmseer.com/1028-0960/article/view/664544
DOI: https://doi.org/10.31857/S1028096023060043
EDN: https://elibrary.ru/DHQHYU
ID: 664544

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Abstract

Osmium compounds with the Os5d⁴ electron configuration and an octahedral environment of neighboring atoms attract much attention due to the influence of the spin-orbit interaction on the appearance of magnetic properties in materials. XANES spectroscopy makes it possible to obtain information about the magnitude of the spin-orbit interaction from measuring the intensity ratio of lines near the absorption edges. The influence of the spin-orbit interaction on the XANES OsL_2,3 spectra in osmium compounds having an octahedral halogen environment of osmium atoms has been studied. Two types of systems have been investigated: isolated osmium clusters in complex compounds and OsCl₄ compound containing polymeric chains of Os connected by bridging Cl atoms. Magnetic susceptibility measurements show a non-magnetic ground state and Van Vleck paramagnetism in the case of isolated clusters and a non-zero magnetic moment over the entire temperature range in OsCl₄. As a result of measurements of the XANES spectra, high values of the line intensity ratio near the OsL₃/L₂ absorption edges have been obtained, which is associated with a strong influence of the spin-orbit interaction on the electronic structure. Theoretical analysis of the XANES spectra of Os compounds with different ligands and outer-sphere cations shows that the electronic structure and magnetic properties depend on the spin-orbit interaction, the crystal field splitting, the electron pairing energy, and non-cubic distortions of the Os environment.

Keywords

spin-orbit interaction, osmium complex compounds, X-ray absorption spectroscopy, magnetic properties, osmium chloride, octahedral complexes, electronic structure, X-ray photoelectron spectroscopy, quantum chemistry, electron correlations.

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