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 .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://journals.rcsi.science/1028-0960/article/view/137761
DOI: https://doi.org/10.31857/S1028096023060043
EDN: https://elibrary.ru/DHQHYU
ID: 137761

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Abstract
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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.

References

Martins C., Aichhorn M., Biermann S. // J. Phys.: Condens. Matter. 2017. V. 29. P. 263001. https://doi.org/10.1088/1361-648X/aa648f
Gotfryd D., Paerschke E.M., Chaloupka J., Oles A.M., Wohlfeld K. // Phys. Rev. Res. 2020. V. 2. P. 013353. https://doi.org/10.1103/PhysRevResearch.2.013353
Khomskii D.I., Streltsov S.V. // Chem. Rev. 2021. V. 121. P. 2992. https://doi.org/10.1021/acs.chemrev.0c00579
Kim B.J., Jin H., Moon S.J., Kim J.-Y., Park B.-G., Leem C.S., Yu J., Noh T.W., Kim C., Oh S.-J., Park J.-H., Durairaj V., Cao G., Rotenberg E. // Phys. Rev. Lett. 2008. V. 101. P. 076402. https://doi.org/10.1103/PhysRevLett.101.076402
Jackeli G., Khaliullin G. // Phys. Rev. Lett. 2009. V. 102. P. 017205. https://doi.org/10.1103/PhysRevLett.102.017205
Khaliullin G. // Phys. Rev. Lett. 2013. V.111. P. 197201. https://doi.org/10.1103/PhysRevLett. 111.197201
Синтез комплексных соединений металлов платиновой группы. Справочник / Ред. Черняев И.И. М.: Наука, 1964. 340 с.
Громилов С.А., Коренев С.В., Храненко С.П., Алексеев В.И. // ЖСХ. 1997. Т. 38. № 1. С. 120. https://doi.org/10.1007/BF02768813
Губанов А.И., Коренев С.В., Громилов С.А., Байдина И.А., Венедиктов А.Б. // ЖСХ. 2000. Т. 41. № 2. С. 417. https://doi.org/10.1007/BF02741603
Корольков И.В., Губанов А.И., Юсенко К.В., Байдина И.А., Громилов С.А. // ЖСХ. 2007. Т. 48. № 3. С. 530. https://doi.org/10.1007/s10947-007-0073-1
Колбин Н.И., Семенов И.Н., Шутов Ю.М. // ЖНХ. 1963. Т. 8. № 11. С. 2422.
Powder Diffraction File (2022) International Centre for Diffraction Data, Pennsylvania, USA.
Clancy J.P., Chen N., Kim C.Y., Chen W.F., Plumb K.W., Jeon B.C., Noh T.W., Kim Y.-J. // Phys. Rev. B. 2012. V. 86. P. 195131. https://doi.org/10.1103/PhysRevB.86.195131
Bunau O., Joly Y. // J. Phys.: Condens. Matter. 2009. V. 21. P. 345501. https://doi.org/10.1088/0953-8984/21/34/345501
Neese F. // WIREs Comput. Mol. Sci. 2018. V. 8. P. e1327. https://doi.org/10.1002/wcms.1327
Weigend F., Ahlrichs R. // Phys. Chem. Chem. Phys. 2005. V. 7. P. 3297. https://doi.org/10.1039/B508541A
Stoychev G.L., Auer A.A., Neese F. // J. Chem. Theory Comput. 2017. V. 13. P. 554. https://doi.org/10.1021/acs.jctc.6b01041
Noro T., Sekiya M., Koga T. // Theo. Chem. Acc. 2013. V. 132. P. 1363. https://doi.org/10.1007/s00214-013-1363-7
Hess B.A. // Phys. Rev. A. 1986. V. 33. P. 3742. https://doi.org/10.1103/PhysRevA.33.3742
Angeli C., Cimiraglia R., Malrieu J.-P. // Chem. Phys. Lett. 2001. V. 350. P. 297. https://doi.org/10.1016/S0009-2614(01)01303-3
Ganyushin D., Neese F. // J. Chem. Phys. 2013. V. 138. P. 104113. https://doi.org/10.1063/1.4793736
Kohlmann H. // Z. Anorg. Allg. Chem. 2022. V. 648. P. e202100375. https://doi.org/10.1002/zaac.202100375
Ivlev S.I., Malin A.V., Karttunen A.J., Ostvald R.V., Kraus F. // J. Fluorine Chem. 2019. V. 218. P. 11. https://doi.org/10.1016/j.jfluchem.2018.11.010
Asanova T.I., Asanov I.P., Yusenko K.V., La Fontaine C., Gerasimov E.Yu., Zadesenets A.V., Korenev S.V. // Mat. Res. Bull. 2021. V. 144. P. 111511. https://doi.org/10.1016/j.materresbull.2021.111511
Громилов С.А., Шубин Ю.В., Губанов А.И., Максимовский Е.А., Коренев С.В. // ЖСХ. 2009. Т. 50. № 6. С. 1174. https://doi.org/10.1007/s10947-009-0164-2
Габуда С.П., Гагаринский Ю.В., Полищук С.А. ЯМР в неорганических фторидах, структура и химическая связь. М.: Атомиздат, 1978. 208 с.
Machmer P. // Z. Naturforsch. B. 1969. V. 24. P. 200. https://doi.org/10.1515/znb-1969-0209
Cotton F.A., Rice C.E. // Inorg. Chem. 1977. V. 16. P. 1865. https://doi.org/10.1021/ic50174a008
Асанова Т.И., Асанов И.П., Ким М.-Г., Коренев С.В. // ЖСХ. 2017. Т. 58. № 5. С. 936. https://doi.org/10.1134/S0022476617050079
Asanova T., Asanov I., Zadesenets A., Filatov E., Plyusnin P., Gerasimov E., Korenev S. // J. Therm. Anal. Calorim. 2016. V. 123. P. 1183. https://doi.org/10.1007/s10973-015-5002-5
Nefedov V.I. // J. Electron Spectrosc. Relat. Phen. 1977. V. 12. P. 459. https://doi.org/10.1016/0368-2048(77)85097-4
Falconer W.E., Disalvo F.J., Griffiths J.E., Stevie F.A., Sunder W.A., Vasile M.J. // J. Fluor. Chem. 1975. V. 6. № 6. P. 499. https://doi.org/10.1002/chin.197604027
Blundell S. Magnetism in Condensed Matter. Oxford: Oxford University Press, 2001. 238 p.
Paramekanti A., Singh D.J., Yuan B., Casa D., Said A., Kim Y.-J., Christianson A.D. // Phys. Rev. B. 2018. V. 97. P. 235119.https://doi.org/10.1103/PhysRevB.97.235119
Stamokostas G.L., Fiete G.A. // Phys. Rev. B. 2018. V. 97. P. 085150. https://doi.org/10.1103/PhysRevB.97.085150