- Physical Review Journals
All JournalsPhysics Magazine

Physical Review Letters

Reuse & Permissions

It is not necessary to obtain permission to reuse this article or its components as it is available under the terms of the Creative Commons Attribution 4.0 International license. This license permits unrestricted use, distribution, and reproduction in any medium, provided attribution to the author(s) and the published article's title, journal citation, and DOI are maintained. Please note that some figures may have been included with permission from other third parties. It is your responsibility to obtain the proper permission from the rights holder directly for these figures.

Export citation

Export citation

Choose format for download:

Download Citation
  • Editors' Suggestion
  • Open Access

Origin of Magnetism in a Supposedly Nonmagnetic Osmium Oxide

S. Agrestini1,*, F. Borgatti2, P. Florio3, J. Frassineti4, D. Fiore Mosca5, Q. Faure6, B. Detlefs6, C. J. Sahle6, S. Francoual7 et al.

J. Choi1, M. Garcia-Fernandez1, K.-J. Zhou1, V. F. Mitrović8, P. M. Woodward9, G. Ghiringhelli3, C. Franchini4, F. Boscherini4, S. Sanna4, and M. Moretti Sala3,†

  • *Contact author: stefano.agrestini@diamond.ac.uk
  • †Contact author: marco.moretti@polimi.it
PDF

Phys. Rev. Lett. 133, 066501 – Published 5 August, 2024

DOI: https://doi.org/10.1103/PhysRevLett.133.066501

Abstract

A supposedly nonmagnetic 5d1 double perovskite oxide is investigated by a combination of spectroscopic and theoretical methods, namely, resonant inelastic x-ray scattering, x-ray absorption spectroscopy, magnetic circular dichroism, and multiplet ligand-field calculations. We found that the large spin-orbit coupling admixes the 5d t2g and eg orbitals, covalency raises the 5d population well above the nominal value, and the local symmetry is lower than Oh. The obtained electronic interactions account for the finite magnetic moment of Os in this compound and, in general, of 5d1 ions. Our results provide direct evidence of elusive Jahn-Teller distortions, hinting at a strong electron-lattice coupling.

View figure in article

Physics Subject Headings (PhySH)

Article Text

Supplemental Material

References (60)

  1. B. J. Kim, H. Jin, S. J. Moon, J.-Y. Kim, B.-G. Park, C. S. Leem, J. Yu, T. W. Noh, C. Kim, S.-J. Oh, J.-H. Park, V. Durairaj, G. Cao, and E. Rotenberg, Novel Jeff=1/2 Mott state induced by relativistic spin-orbit coupling in Sr2IrO4, Phys. Rev. Lett. 101, 076402 (2008).
  2. B. J. Kim, H. Ohsumi, T. Komesu, S. Sakai, T. Morita, H. Takagi, and T. Arima, Phase-sensitive observation of a spin-orbital Mott state in Sr2IrO4, Science 323, 1329 (2009).
  3. W. Witczak-Krempa, G. Chen, Y. B. Kim, and L. Balents, Correlated quantum phenomena in the strong spin-orbit regime, Annu. Rev. Condens. Matter Phys. 5, 57 (2014).
  4. G. Jackeli and G. Khaliullin, Mott insulators in the strong spin-orbit coupling limit: From Heisenberg to a quantum compass and Kitaev models, Phys. Rev. Lett. 102, 017205 (2009).
  5. J. G. Rau, E. K.-H. Lee, and H.-Y. Kee, Spin-orbit physics giving rise to novel phases in correlated systems: Iridates and related materials, Annu. Rev. Condens. Matter Phys. 7, 195 (2016).
  6. S. M. Winter, A. A. Tsirlin, M. Daghofer, J. van den Brink, Y. Singh, P. Gegenwart, and R. Valentí, Models and materials for generalized Kitaev magnetism, J. Phys. Condens. Matter 29, 493002 (2017).
  7. G. Cao and P. Schlottmann, The challenge of spin–orbit-tuned ground states in iridates: A key issues review, Rep. Prog. Phys. 81, 042502 (2018).
  8. H. Liu and G. Khaliullin, Pseudo-Jahn-Teller effect and magnetoelastic coupling in spin-orbit Mott insulators, Phys. Rev. Lett. 122, 057203 (2019).
  9. S. V. Streltsov and D. I. Khomskii, Jahn-Teller effect and spin-orbit coupling: Friends or foes?, Phys. Rev. X 10, 031043 (2020).
  10. S. V. Streltsov, F. V. Temnikov, K. I. Kugel, and D. I. Khomskii, Interplay of the Jahn-Teller effect and spin-orbit coupling: The case of trigonal vibrations, Phys. Rev. B 105, 205142 (2022).
  11. K. E. Stitzer, M. D. Smith, and H.-C. zur Loye, Crystal growth of Ba2MOsO6 (M=Li, Na) from reactive hydroxide fluxes, Solid State Sci. 4, 311 (2002).
  12. L. Xu, N. Bogdanov, A. A Princep, P. Fulde, J. van den Brink, and L. Hozoi, Covalency and vibronic couplings make a nonmagnetic j= 3/2 ion magnetic, npj Quantum Mater. 1, 16029 (2016).
  13. N. Iwahara, V. Vieru, and L. F. Chibotaru, Spin-orbital-lattice entangled states in cubic d1 double perovskites, Phys. Rev. B 98, 075138 (2018).
  14. A. S. Erickson, S. Misra, G. J. Miller, R. R. Gupta, Z. Schlesinger, W. A. Harrison, J. M. Kim, and I. R. Fisher, Ferromagnetism in the Mott insulator Ba2NaOsO6, Phys. Rev. Lett. 99, 016404 (2007).
  15. H. J. Xiang and M.-H. Whangbo, Cooperative effect of electron correlation and spin-orbit coupling on the electronic and magnetic properties of Ba2NaOsO6, Phys. Rev. B 75, 052407 (2007).
  16. K.-W. Lee and W. E. Pickett, Orbital-quenching–induced magnetism in Ba2NaOsO6, Europhys. Lett. 80, 37008 (2007).
  17. R. Cong, R. Nanguneri, B. Rubenstein, and V. F. Mitrović, Evidence from first-principles calculations for orbital ordering in Ba2NaOsO6: A Mott insulator with strong spin-orbit coupling, Phys. Rev. B 100, 245141 (2019).
  18. M. Kotani, On the magnetic moment of complex ions (I), J. Phys. Soc. Jpn. 4, 293 (1949).
  19. A. Abragam and B. Bleaney, Electron Paramagnetic Resonance of Transition Ions (Clarendon Press, Oxford, 1970), pp. 417–426.
  20. F. E. Mabbs and D. J. Machin, Magnetism and Transition Metal Complexes (Chapman and Hall, London, 1973), pp. 68–84.
  21. R. Cong, E. Garcia, P. C. Forino, A. Tassetti, G. Allodi, A. P. Reyes, P. M. Tran, P. M. Woodward, C. Franchini, S. Sanna, and V. F. Mitrović, Effects of charge doping on Mott insulator with strong spin-orbit coupling, Ba2Na1−xCaxOsO6, Phys. Rev. Mater. 7, 084409 (2023).
  22. D. Fiore Mosca, L. V. Pourovskii, B. H. Kim, P. Liu, S. Sanna, F. Boscherini, S. Khmelevskyi, and C. Franchini, Interplay between multipolar spin interactions, Jahn-Teller effect, and electronic correlation in a Jeff=32 insulator, Phys. Rev. B 103, 104401 (2021).
  23. K.-H. Ahn, K. Pajskr, K.-W. Lee, and J. Kuneš, Calculated g-factors of 5d double perovskites Ba2NaOsO6 and Ba2YOsO6, Phys. Rev. B 95, 064416 (2017).
  24. L. Lu, M. Song, W. Liu, A. P. Reyes, P. Kuhns, H. O. Lee, I. R. Fisher, and V. F. Mitrović, Magnetism and local symmetry breaking in a Mott insulator with strong spin orbit interactions, Nat. Commun. 8, 14407 (2017).
  25. K. Willa, R. Willa, U. Welp, I. R. Fisher, A. Rydh, W.-K. Kwok, and Z. Islam, Phase transition preceding magnetic long-range order in the double perovskite Ba2NaOsO6, Phys. Rev. B 100, 041108(R) (2019).
  26. V. da Cruz Pinha Barbosa, J. Xiong, P. M. Tran, M. A. McGuire, J. Yan, M. T. Warren, R. V. Aguilar, W. Zhang, M. Randeria, N. Trivedi, D. Haskel, and P. M. Woodward, The impact of structural distortions on the magnetism of double perovskites containing 5d1 transition-metal ions, Chem. Mater. 34, 1098 (2022).
  27. J. K. Kesavan, D. Fiore Mosca, S. Sanna, F. Borgatti, G. Schuck, P. M. Tran, P. M. Woodward, V. F. Mitrović, C. Franchini, and F. Boscherini, Doping evolution of the local electronic and structural properties of the double perovskite Ba2Na1−xCaxOsO6, J. Phys. Chem. C 124, 16577 (2020).
  28. M. Moretti Sala, K. Martel, C. Henriquet, A. Al Zein, L. Simonelli, C. J. Sahle, H. Gonzalez, M.-C. Lagier, C. Ponchut, S. Huotari, R. Verbeni, M. Krisch, and G. Monaco, A high-energy-resolution resonant inelastic x-ray scattering spectrometer at ID20 of the European Synchrotron Radiation Facility, J. Synchrotron Radiat. 25, 580 (2018).
  29. K.-J. Zhou, A. Walters, M. Garcia-Fernandez, T. Rice, M. Hand, A. Nag, J. Li, S. Agrestini, P. Garland, H. Wang, S. Alcock, I. Nistea, B. Nutter, N. Rubies, G. Knap, M. Gaughran, F. Yuan, P. Chang, J. Emmins, and G. Howell, I21: An advanced high-resolution resonant inelastic x-ray scattering beamline at Diamond Light Source, J. Synchrotron Radiat. 29, 563 (2022).
  30. J. Strempfer, S. Francoual, D. Reuther, D. K. Shukla, A. Skaugen, H. Schulte-Schrepping, T. Kracht, and H. Franz, Resonant scattering and diffraction beamline P09 at PETRA III, J. Synchrotron Radiat. 20, 541 (2013).
  31. J. Strempfer, J. R. L. Mardegan, S. Francoual, L. S. I. Veiga, L. Bouchenoire, T. Spitzbart, and H. Zink, Fast helicity switching of x-ray circular polarization at beamline P09 at PETRA III, AIP Conf. Proc. 1741, 030017 (2016).
  32. M. W. Haverkort, M. Zwierzycki, and O. K. Andersen, Multiplet ligand-field theory using Wannier orbitals, Phys. Rev. B 85, 165113 (2012).
  33. Y. Lu, M. Höppner, O. Gunnarsson, and M. W. Haverkort, Efficient real-frequency solver for dynamical mean-field theory, Phys. Rev. B 90, 085102 (2014).
  34. M. W. Haverkort, G. Sangiovanni, P. Hansmann, A. Toschi, Y. Lu, and S. Macke, Bands, resonances, edge singularities and excitons in core level spectroscopy investigated within the dynamical mean-field theory, Europhys. Lett. 108, 57004 (2014).
  35. M. M. Sala, V. Bisogni, C. Aruta, G. Balestrino, H. Berger, N. B. Brookes, G. M. de Luca, D. D. Castro, M. Grioni, M. Guarise, P. G. Medaglia, F. M. Granozio, M. Minola, P. Perna, M. Radovic, M. Salluzzo, T. Schmitt, K. J. Zhou, L. Braicovich, and G. Ghiringhelli, Energy and symmetry of dd excitations in undoped layered cuprates measured by Cu L3 resonant inelastic x-ray scattering, New J. Phys. 13, 043026 (2011).

  36. OsO6 cluster parameters [eV]: Udd=1.0, Upd=3.0, charge transfer energy ΔCT=−4.0, spin-orbit coupling λ=0.41, ionic crystal field 10  Dqion=3.3, Δt2gion=−0.25, and Δegion=−0.5, hybridization V(eg)=6.2 and V(t2g)=3.5, and ligand crystal field 10  Dqlig=0.95. Slater integrals were reduced to 70% of the Hartree-Fock values. For all simulations, we have considered the thermal population of the electronic state using the Boltzmann distribution.

  37. H. Ishikawa, T. Takayama, R. K. Kremer, J. Nuss, R. Dinnebier, K. Kitagawa, K. Ishii, and H. Takagi, Ordering of hidden multipoles in spin-orbit entangled 5d1 Ta chlorides, Phys. Rev. B 100, 045142 (2019).
  38. T. Mizokawa, H. Namatame, A. Fujimori, K. Akeyama, H. Kondoh, H. Kuroda, and N. Kosugi, Origin of the band gap in the negative charge-transfer-energy compound NaCuO2, Phys. Rev. Lett. 67, 1638 (1991).
  39. D. Khomskii, Unusual valence, negative charge-transfer gaps and self-doping in transition-metal compounds, arXiv:cond-mat/0101164.
  40. See Supplemental Material at http://link.aps.org/supplemental/10.1103/PhysRevLett.133.066501 for further information, which includes Refs. [41–43].
  41. C. Piamonteze, P. Miedema, and F. M. F. de Groot, Accuracy of the spin sum rule in XMCD for the transition-metal l edges from manganese to copper, Phys. Rev. B 80, 184410 (2009).
  42. M. A. Laguna-Marco, D. Haskel, N. Souza-Neto, J. C. Lang, V. V. Krishnamurthy, S. Chikara, G. Cao, and M. van Veenendaal, Orbital magnetism and spin-orbit effects in the electronic structure of BaIrO3, Phys. Rev. Lett. 105, 216407 (2010).
  43. M. A. Laguna-Marco, P. Kayser, J. A. Alonso, M. J. Martínez-Lope, M. van Veenendaal, Y. Choi, and D. Haskel, Electronic structure, local magnetism, and spin-orbit effects of Ir(IV)-, Ir(V)-, and Ir(VI)-based compounds, Phys. Rev. B 91, 214433 (2015).
  44. A. Rogalev and F. Wilhelm, Magnetic circular dichroism in the hard x-ray range, Phys. Met. Metallogr. 116, 1285 (2015).
  45. L. S. I. Veiga, G. Fabbris, M. van Veenendaal, N. M. Souza-Neto, H. L. Feng, K. Yamaura, and D. Haskel, Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3d−5d double perovskite Sr2FeOsO6, Phys. Rev. B 91, 235135 (2015).
  46. B. T. Thole, P. Carra, F. Sette, and G. van der Laan, X-ray circular dichroism as a probe of orbital magnetization, Phys. Rev. Lett. 68, 1943 (1992).
  47. P. Carra, B. T. Thole, M. Altarelli, and X. Wang, X-ray circular dichroism and local magnetic fields, Phys. Rev. Lett. 70, 694 (1993).
  48. W. Liu, R. Cong, A. P. Reyes, I. R. Fisher, and V. F. Mitrović, Nature of lattice distortions in the cubic double perovskite Ba2NaOsO6, Phys. Rev. B 97, 224103 (2018).
  49. I. Bersuker, The Jahn-Teller Effect (Cambridge University Press, Cambridge, England, 2006), 10.1017/CBO9780511524769.
  50. F. I. Frontini, G. H. J. Johnstone, N. Iwahara, P. Bhattacharyya, N. A. Bogdanov, L. Hozoi, M. H. Upton, D. M. Casa, D. Hirai, and Y.-J. Kim, Spin-orbit-lattice entangled state in A2MgReO6 (A=Ca, Sr, Ba) revealed by resonant inelastic x-ray scattering, Phys. Rev. Lett. 133, 036501 (2024).
  51. N. Iwahara and S. Shikano, Vibronic excitations in resonant inelastic x-ray scattering spectra of K2RuCl6, Phys. Rev. Res. 5, 023051 (2023).
  52. N. Iwahara and L. F. Chibotaru, Vibronic order and emergent magnetism in cubic d1 double perovskites, Phys. Rev. B 107, L220404 (2023).
  53. T. Aharen, J. E. Greedan, C. A. Bridges, A. A. Aczel, J. Rodriguez, G. MacDougall, G. M. Luke, T. Imai, V. K. Michaelis, S. Kroeker, H. Zhou, C. R. Wiebe, and L. M. D. Cranswick, Magnetic properties of the geometrically frustrated s=12 antiferromagnets, La2LiMoO6 and Ba2YMoO6, with the b-site ordered double perovskite structure: Evidence for a collective spin-singlet ground state, Phys. Rev. B 81, 224409 (2010).
  54. H. Ishikawa, T. Yajima, A. Matsuo, and K. Kindo, Ligand dependent magnetism of the jeff=3/2 Mott insulator Cs2MX6 (M=Ta, Nb, X=Br, Cl), J. Phys. Condens. Matter 33, 125802 (2021).
  55. A. J. Steele, P. J. Baker, T. Lancaster, F. L. Pratt, I. Franke, S. Ghannadzadeh, P. A. Goddard, W. Hayes, D. Prabhakaran, and S. J. Blundell, Low-moment magnetism in the double perovskites Ba2MOsO6 (m=Li, Na), Phys. Rev. B 84, 144416 (2011).
  56. K. Yamamura, M. Wakeshima, and Y. Hinatsu, Structural phase transition and magnetic properties of double perovskites Ba2CaMO6 (M=W, Re, Os), J. Solid State Chem. 179, 605 (2006).
  57. A. Mansouri Tehrani and N. A. Spaldin, Untangling the structural, magnetic dipole, and charge multipolar orders in Ba2MgReO6, Phys. Rev. Mater. 5, 104410 (2021).
  58. E. J. Cussen, D. R. Lynham, and J. Rogers, Magnetic order arising from structural distortion: Structure and magnetic properties of Ba2LnMoO6, Chem. Mater. 18, 2855 (2006).
  59. C. R. Wiebe, J. E. Greedan, G. M. Luke, and J. S. Gardner, Spin-glass behavior in the s=1/2 fcc ordered perovskite Sr2CaO6, Phys. Rev. B 65, 144413 (2002).
  60. C. R. Wiebe, J. E. Greedan, P. P. Kyriakou, G. M. Luke, J. S. Gardner, A. Fukaya, I. M. Gat-Malureanu, P. L. Russo, A. T. Savici, and Y. J. Uemura, Frustration-driven spin freezing in the s=1/2 fcc perovskite Sr2MgReO6, Phys. Rev. B 68, 134410 (2003).

Outline

Information

Phys. Rev. Lett. 133, 066501– Published 5 August, 2024
  • Received 23 January 2024
  • Revised 15 April 2024
  • Accepted 1 July 2024
Article part of CHORUS
Crossmark - Check for updates button
Creative Commons Logo

Published by the American Physical Society under the terms of the Creative Commons Attribution 4.0 International license. Further distribution of this work must maintain attribution to the author(s) and the published article’s title, journal citation, and DOI.

Published by the American Physical Society

Sign In to Your Journals Account

Filter

Filter

Article Lookup

Enter a citation