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Orbital-resolved spin-exchange interactions and spin-phonon coupling in CrVO4

Ganesh Bera1,2,*, Sourav Dey3, José J. Baldoví3, Josep Mas-Garcia4, Alejandro Molina-Sánchez4, David Santamaria-Perez1, Daniel Errandonea1, Archna Sagdeo5,6, G. R. Turpu7 et al.

V. G. Sathe2, V. Raghavendra Reddy2, and Carlo Meneghini8,†

  • *Contact author: ganeshbera90@gmail.com, ganesh@uv.es
  • †Contact author: carlo.meneghini@uniroma3.it
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Phys. Rev. Research 7, 043189 – Published 20 November, 2025

DOI: https://doi.org/10.1103/kxbt-1nbq

Abstract

This report investigates the role of orbital degrees of freedom in CrVO4, focusing on orbital-driven spin-exchange interactions and spin-phonon coupling through both experiments and first-principles calculations. Combining synchrotron radiation x-ray powder diffraction, Raman spectroscopy, and x-ray absorption fine structure measurements, a significant correlation between magnetic transition and structural modification was identified, revealing spin-lattice coupling at the transition (TN). This coupling is linked to conventional magnetoelastic interactions, even active above TN, supported by both experimental and theoretical findings. The calculations revealed crystal field splitting and orbital nondegeneracy resulting from charge transfer in the 3d3 system of CrVO4 due to octahedral symmetry breaking. The study discusses the detailed mechanism of orbital-resolved spin-exchange interactions, leading to one-dimensional A-type antiferromagnetic ordering. Notably, no significant orbital-selective spin-phonon coupling was observed at approximately 200 K (4TN) in CrVO4, in contrast to earlier studies [A. P. Roy et al., Phys. Rev. Lett. 132, 026701 (2024)]. These findings advance the understanding of the fundamental physics in CrVO4 and significantly contribute to the field of spin-orbital-lattice physics in transition metal oxides.

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References (91)

  1. S. V. Streltsov and D. I. Khomskii, Orbital physics in transition metal compounds: new trends, Phys. Usp. 60, 1121 (2017).
  2. K. I. Kugel' and D. I. Khomskiĭ, The Jahn-Teller effect and magnetism: Transition metal compounds, Sov. Phys. Usp. 25, 231 (1982).
  3. Y. Tokura and N. Nagaosa, Orbital physics in transition-metal oxides, Science 288, 462 (2000).
  4. R. Logemann, A. N. Rudenko, M. I. Katsnelson, and A. Kirilyuk, Exchange interactions in transition metal oxides: The role of oxygen spin polarization, J. Phys.: Condens. Matter 29, 335801 (2017).
  5. M. Grüninger, R. Rückamp, M. Windt, P. Reutler, C. Zobel, T. Lorenz, A. Freimuth, and A. Revcolevschi, Experimental quest for orbital waves, Nature (London) 418, 39 (2002).
  6. C. Ulrich, A. Gössling, M. Grüninger, M. Guennou, H. Roth, M. Cwik, T. Lorenz, G. Khaliullin, and B. Keimer, Raman scattering in the Mott insulators LaTiO3 and YTiO3: Evidence for orbital excitations, Phys. Rev. Lett. 97, 157401 (2006).
  7. Y. Murakami, H. Kawada, H. Kawata, M. Tanaka, T. Arima, Y. Moritomo, and Y. Tokura, Direct observation of charge and orbital ordering in La0.5Sr1.5MnO4, Phys. Rev. Lett. 80, 1932 (1998).
  8. S. Sugai and K. Hirota, Orbital waves in YVO3 studied by Raman scattering, Phys. Rev. B 73, 020409 (2006).
  9. T. Hotta, Orbital ordering phenomena in d- and f-electron systems, Rep. Prog. Phys. 69, 2061 (2006).
  10. S. V. Streltsov and D. I. Khomskii, Jahn-Teller effect and spin-orbit coupling: Friends or foes? Phys. Rev. X 10, 031043 (2020).
  11. N. Iwahara, V. Vieru, and L. F. Chibotaru, Spin-orbital-lattice entangled states in cubic d1 double perovskites, Phys. Rev. B 98, 075138 (2018).
  12. J. Romhányi, L. Balents, and G. Jackeli, Spin-orbit dimers and noncollinear phases in d1 cubic double perovskites, Phys. Rev. Lett. 118, 217202 (2017).
  13. 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= 3/2 insulator, Phys. Rev. B 103, 104401 (2021).
  14. H. Watanabe, T. Shirakawa, and S. Yunoki, Microscopic study of a spin-orbit-induced Mott insulator in Ir oxides, Phys. Rev. Lett. 105, 216410 (2010).
  15. M. Z. Hasan and C. L. Kane, Colloquium: Topological insulators, Rev. Mod. Phys. 82, 3045 (2010).
  16. X.-L. Qi and S.-C. Zhang, Topological insulators and superconductors, Rev. Mod. Phys. 83, 1057 (2011).
  17. Z. K. Liu, B. Zhou, Y. Zhang, Z. J. Wang, H. M. Weng, D. Prabhakaran, S.-K. Mo, Z. X. Shen, Z. Fang, X. Dai, Z. Hussain, and Y. L. Chen, Discovery of a three-dimensional topological Dirac semimetal, Na3Bi, Science 343, 864 (2014).
  18. S.-Y. Xu et al., Discovery of a Weyl fermion semimetal and topological Fermi arcs, Science 349, 613 (2015).
  19. Y. Tokura, S. Seki, and N. Nagaosa, Multiferroics of spin origin, Rep. Prog. Phys. 77, 076501 (2014).
  20. R. Rejali, D. Coffey, J. Gobeil, J. W. González, F. Delgado, and A. F. Otte, Complete reversal of the atomic unquenched orbital moment by a single electron, npj Quantum Mater. 5, 60 (2020).
  21. A. M. León, J. W. González, and H. Rosner, Ca3Ru2O7: Interplay among degrees of freedom and the role of the exchange correlation, Phys. Rev. Mater. 8, 024411 (2024).
  22. J. B. Goodenough, Magnetism and the Chemical Bond (Wiley-Interscience Publishers, New York, 1963).
  23. T. Knaflič, P. Jeglič, M. Komelj, A. Zorko, P. K. Biswas, A. N. Ponomaryov, S. A. Zvyagin, M. Reehuis, A. Hoser, M. Geiss, J. Janek, P. Adler, C. Felser, M. Jansen, and D. Arčon, Spin-dimer ground state driven by consecutive charge and orbital ordering transitions in the anionic mixed-valence compound Rb4O6, Phys. Rev. B 101, 024419 (2020).
  24. V. Kocsis, Y. Tokunaga, T. Rõõm, U. Nagel, J. Fujioka, Y. Taguchi, Y. Tokura, and S. Bordács, Spin-lattice and magnetoelectric couplings enhanced by orbital degrees of freedom in polar multiferroic semiconductors, Phys. Rev. Lett. 130, 036801 (2023).
  25. A. S. Disa, J. Curtis, M. Fechner, A. Liu, A. von Hoegen, M. Först, T. F. Nova, P. Narang, A. Maljuk, A. V. Boris, B. Keimer, and A. Cavalleri, Photo-induced high-temperature ferromagnetism in YTiO3, Nature (London) 617, 73 (2023).
  26. A. B. Harris, T. Yildirim, A. Aharony, O. Entin-Wohlman, and I. Y. Korenblit, Unusual symmetries in the Kugel-Khomskii Hamiltonian, Phys. Rev. Lett. 91, 087206 (2003).
  27. G. Bera, V. R. Reddy, P. Rambabu, P. Mal, P. Das, N. Mohapatra, G. Padmaja, and G. R. Turpu, Triclinic–monoclinic–orthorhombic (T–M–O) structural transitions in phase diagram of FeVO4−CrVO4 solid solutions, J. Appl. Phys. 122, 115101 (2017).
  28. E. J. Baran, Materials belonging to the CrVO4 structure type: Preparation, crystal chemistry and physicochemical properties, J. Mater. Sci. 33, 2479 (1998).
  29. B. C. Frazer and P. J. Brown, Antiferromagnetic structure of CrVO4 and the anhydrous sulfates of divalent Fe, Ni, and Co, Phys. Rev. 125, 1283 (1962).
  30. G. Bera, A. Surampalli, A. Mishra, P. Mal, V. R. Reddy, A. Banerjee, A. Sagdeo, P. Das, and G. R. Turpu, Magnetolattice coupling, magnetic frustration, and magnetoelectric effect in the Cr-doped FeVO4 multiferroic material and their correlation with structural phase transitions, Phys. Rev. B 100, 014436 (2019).
  31. H. J. Koo, M. H. Whangbo, and K. S. Lee, Investigation of the spin exchange interactions and magnetic structures of the CrVO4-type transition metal phosphates, sulfates, and vanadates by spin dimer analysis, Inorg. Chem. 42, 5932 (2003).
  32. H. Saji, T. Yamadaya, and M. Asanuma, Nuclear magnetic resonance study of V51 in CrVO4, Phys. Lett. A 34, 49 (1971).
  33. M. J. Isasi, R. Sáez-Puche, M. L. Veiga, C. Pico, and A. Jerez, Synthesis and magnetic properties of crystalline CrVO4, Mater. Res. Bull. 23, 595 (1988).
  34. K. I. Kugel and D. I. Khomskii, Crystal-structure and magnetic properties of substances with orbital degeneracy, Zh. Eksp. Teor. Fiz. 64, 1429 (1973) [Sov. Phys. JETP 37, 725 (1973)].
  35. E. Pavarini and E. Koch, Origin of Jahn-Teller distortion and orbital order in LaMnO3, Phys. Rev. Lett. 104, 086402 (2010).
  36. M. Kim and B. I. Min, Temperature-dependent orbital physics in a spin-orbital-lattice-coupled 2 p electron Mott system: The case of KO2, Phys. Rev. B 89, 121106 (2014).
  37. G. Khaliullin, D. Churchill, P. P. Stavropoulos, and H.-Y. Kee, Exchange interactions, Jahn-Teller coupling, and multipole orders in pseudospin one-half 5d2 Mott insulators, Phys. Rev. Res. 3, 033163 (2021).
  38. E. Pavarini, E. Koch, and A. I. Lichtenstein, Mechanism for orbital ordering in KCuF3, Phys. Rev. Lett. 101, 266405 (2008).
  39. X.-J. Zhang, E. Koch, and E. Pavarini, LaVO3: A true Kugel-Khomskii system, Phys. Rev. B 106, 115110 (2022).
  40. X.-J. Zhang, E. Koch, and E. Pavarini, Origin of orbital ordering in YTiO3 and LaTiO3, Phys. Rev. B 102, 035113 (2020).
  41. W. Brzezicki, J. Dziarmaga, and A. M. Oleś, Exotic spin orders driven by orbital fluctuations in the Kugel-Khomskii model, Phys. Rev. B 87, 064407 (2013).
  42. A. Koga, S. Nakauchi, and J. Nasu, Role of spin-orbit coupling in the Kugel-Khomskii model on the honeycomb lattice, Phys. Rev. B 97, 094427 (2018).
  43. I. V. Solovyev, R. Ono, and S. A. Nikolaev, Ferromagnetic ferroelectricity due to the Kugel-Khomskii mechanism of orbital ordering assisted by atomic Hund’s second rule effects, Phys. Rev. B 110, 205116 (2024).
  44. A. P. Roy, Jayakrishnan SS, V. Dwij, A. Khandelwal, M. K. Chattopadhyay, V. Sathe, R. Mittal, P. U. Sastry, S. N. Achary, A. K. Tyagi, P. D. Babu, M. D. Le, and D. Bansal, Evidence of strong orbital-selective spin-orbital-phonon coupling in CrVO4, Phys. Rev. Lett. 132, 026701 (2024).
  45. J. Laverdière, S. Jandl, A. A. Mukhin, V. Yu. Ivanov, V. G. Ivanov, and M. N. Iliev, Spin-phonon coupling in orthorhombic RMnO3 (R = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Y): A Raman study, Phys. Rev. B 73, 214301 (2006).
  46. E. Granado, A. García, J. A. Sanjurjo, C. Rettori, I. Torriani, F. Prado, R. D. Sánchez, A. Caneiro, and S. B. Oseroff, Magnetic ordering effects in the Raman spectra of La1−xMn1−xO3, Phys. Rev. B 60, 11879 (1999).
  47. B. Poojitha, A. Rathore, A. Kumar, and S. Saha, Signatures of magnetostriction and spin-phonon coupling in magnetoelectric hexagonal R15−BaMnO3, Phys. Rev. B 102, 134436 (2020).
  48. C. Meneghini, S. Mobilio, F. Bardelli, and C. Prestipino, ESTRA and FitEXA, in International Tables for Crystallography, Volume I: X-Ray Absorption Spectroscopy and Related Techniques, edited by C. T. Chantler, F. Boscherini, and B. Bunker (International Union of Crystallography, 2024), Chap. 6.3, pp. 734–738.
  49. J. J. Rehr and R. C. Albers, Theoretical approaches to x-ray absorption fine structure, Rev. Mod. Phys. 72, 621 (2000).
  50. A. L. Ankudinov, B. Ravel, J. J. Rehr, and S. D. Conradson, Real-space multiple-scattering calculation and interpretation of x-ray-absorption near-edge structure, Phys. Rev. B 58, 7565 (1998).
  51. G. Bera, A. Surampalli, M. L. Riddick, V. R. Reddy, V. G. Sathe, G. R. Turpu, E. Welter, A. Sagdeo, and C. Meneghini, Local structural investigation across the magnetic transition in the type-II multiferroic material FeOO4, Phys. Rev. B 109, 075138 (2024).
  52. G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47, 558 (1993).
  53. G. Kresse and J. Furthmüller, Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set, Comput. Mater. Sci. 6, 15 (1996).
  54. G. Kresse and J. Furthmüller, Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set, Phys. Rev. B 54, 11169 (1996).
  55. H. J. Monkhorst and J. D. Pack, Special points for Brillouin-zone integrations, Phys. Rev. B 13, 5188 (1976).
  56. J. P. Perdew, A. Ruzsinszky, G. I. Csonka, O. A. Vydrov, G. E. Scuseria, L. A. Constantin, X. Zhou, and K. Burke, Restoring the density-gradient expansion for exchange in solids and surfaces, Phys. Rev. Lett. 100, 136406 (2008).
  57. S. L. Dudarev, G. A. Botton, S. Y. Savrasov, C. J. Humphreys, and A. P. Sutton, Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study, Phys. Rev. B 57, 1505 (1998).
  58. C. Gray, Y. Lei, and G. Wang, Charged vacancy diffusion in chromium oxide crystal: DFT and DFT+U predictions, J. Appl. Phys. 120, 215101 (2016).
  59. M.-H. Whangbo, H.-J. Koo, and R. K. Kremer, Spin exchanges between transition metal ions governed by the ligand p-orbitals in their magnetic orbitals, Molecules 26, 531 (2021).
  60. M. Musa Saad H.-E. and Ahmed Elhag, DFT study on the crystal, electronic and magnetic structures of tantalum based double perovskite oxides Ba2MTaO6 (M = Cr, Mn, Fe) via GGA and GGA+U, Results Phys. 9, 793 (2018).
  61. P. Botella, S. López-Moreno, D. Errandonea, F.-J. Manjón, J. A. Sans, D. Vie, and A. Vomiero, High-pressure characterization of multifunctional CrVO4, J. Phys.: Condens. Matter 32, 385403 (2020).
  62. J. M. Skelton, L. A. Burton, A. J. Jackson, F. Oba, S. C. Parker, and A. Walsh, Lattice dynamics of the tin sulphides SnS2, SnS, and Sn2S3: Vibrational spectra and thermal transport, Phys. Chem. Chem. Phys. 19, 12452 (2017).
  63. A. A. Mostofi, J. R. Yates, Y.-S. Lee, I. Souza, D. Vanderbilt, and N. Marzari, Wannier90: A tool for obtaining maximally-localised Wannier functions, Comput. Phys. Commun. 178, 685 (2008).
  64. X. He, N. Helbig, M. J. Verstraete, and E. Bousquet, TB2J: A python package for computing magnetic interaction parameters, Comput. Phys. Commun. 264, 107938 (2021).
  65. S. Toth and B. Lake, Linear spin wave theory for single-Q incommensurate magnetic structures, J. Phys.: Condens. Matter 27, 166002 (2015).
  66. See Supplemental Material at http://link.aps.org/supplemental/10.1103/kxbt-1nbq for the details of magnon dispersion, Fig. S1 - Fig. S17, and Table SI - Table SV along with references.
  67. F. Aquilante et al., Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table, Table. J. Comput. Chem. 37, 506 (2016).
  68. B. O. Roos, R. Lindh, P.-Å. Malmqvist, V. Veryazov, and P.-O. Widmark, Main group atoms and dimers studied with a new relativistic ANO basis set, J. Phys. Chem. A 108, 2851 (2004).
  69. B. O. Roos, R. Lindh, P.-Å. Malmqvist, V. Veryazov, P.-O. Widmark, and A. C. Borin, New relativistic atomic natural orbital basis sets for lanthanide atoms with applications to the Ce diatom and LuF3, J. Phys. Chem. A 112, 11431 (2008).
  70. M. Reiher, Douglas-Kroll-Hess theory: A relativistic electrons-only theory for chemistry, Theor. Chem. Acc. 116, 241 (2006).
  71. P. Å. Malmqvist, B. O. Roos, and B. Schimmelpfennig, The restricted active space (RAS) state interaction approach with spin-orbit coupling, Chem. Phys. Lett. 357, 230 (2002).
  72. M. Benfatto and C. Meneghini, A close look into the low energy region of the XAS spectra: The XANES region, in Synchrotron Radiation: Basics, Methods and Applications, edited by S. Mobilio, F. Boscherini, and C. Meneghini (Springer, Berlin, Heidelberg, 2014), pp. 213–240.
  73. J. Kanamori, Superexchange interaction and symmetry properties of electron orbitals, J. Phys. Chem. Solids 10, 87 (1959).
  74. J. B. Goodenough, Theory of the role of covalence in the perovskite-type manganites [La, M (II)]MnO3, Phys. Rev. 100, 564 (1955).
  75. P. J. Hay, J. C. Thibeault, and R. Hoffmann, Orbital interactions in metal dimer complexes, J. Am. Chem. Soc. 97, 4884 (1975).
  76. H. Xiang, C. Lee, H.-J. Koo, X. Gong, and M.-H. Whangbo, Magnetic properties and energy-mapping analysis, Dalton Trans. 42, 823 (2013).
  77. K. Ghoshray, B. Pahari, B. Bandyopadhyay, R. Sarkar, and A. Ghoshray, V51 NMR study of the quasi-one-dimensional alternating chain compound BaCu2V2O8, Phys. Rev. B 71, 214401 (2005).
  78. A. M. Golubev, J. Nuss, R. K. Kremer, E. E. Gordon, M.-H. Whangbo, C. Ritter, L. Weber, and S. Wessel, Two-dimensional magnetism in α−CuV2O6, Phys. Rev. B 102, 014436 (2020).
  79. A. N. Vasil'ev, L. A. Ponomarenko, H. Manaka, I. Yamada, M. Isobe, and Y. Ueda, Quasi-one-dimensional antiferromagnetic spinel compound LiCuVO4, Phys. B: Condens. Matter 284–288, 1619 (2000).
  80. A. N. Vasil’ev, L. A. Ponomarenko, H. Manaka, I. Yamada, M. Isobe, and Y. Ueda, Magnetic and resonant properties of quasi-one-dimensional antiferromagnet LiCuVO4, Phys. Rev. B 64, 024419 (2001).
  81. S. Saha, S. Singh, B. Dkhil, S. Dhar, R. Suryanarayanan, G. Dhalenne, A. Revcolevschi, and A. K. Sood, Temperature-dependent Raman and x-ray studies of the spin-ice pyrochlore Dy2Ti2O7 and nonmagnetic pyrochlore Lu2Ti2O7, Phys. Rev. B 78, 214102 (2008).
  82. A. Tiwari, D. C. Kakarla, B. Poojitha, P. Sahoo, H. L. Liu, A. Dixit, C. W. Wang, T. W. Yen, M.-J. Hsieh, J.-Y. Lin, J. Krishnamurthy, Y. C. Lai, H. Chou, T. W. Kuo, A. Pal, and H. D. Yang, Spin-phonon-charge coupling in the two-dimensional honeycomb lattice compound Ni2Te3O8, Phys. Rev. B 108, 075113 (2023).
  83. M. Balkanski, R. F. Wallis, and E. Haro, Anharmonic effects in light scattering due to optical phonons in silicon, Phys. Rev. B 28, 1928 (1983).
  84. S. Badola, S. Mukherjee, G. Sunil, B. Ghosh, D. Negi, G. Vaitheeswaran, A. C. Garcia-Castro, and S. Saha, Spin-phonon coupling suppressing the structural transition in perovskite-like oxide, Phys. Rev. B 109, L060104 (2024).
  85. M. G. Cottam and D. J. Lockwood, Spin-phonon interaction in transition-metal difluoride antiferromagnets: Theory and experiment, Low Temp. Phys. 45, 78 (2019).
  86. D. J. Lockwood and M. G. Cottam, The spin-phonon interaction in FeF2 and MnF2 studied by Raman spectroscopy, J. Appl. Phys. 64, 5876 (1988).
  87. E. Aytan, B. Debnath, F. Kargar, Y. Barlas, M. M. Lacerda, J. X. Li, R. K. Lake, J. Shi, and A. A. Balandin, Spin-phonon coupling in antiferromagnetic nickel oxide, Appl. Phys. Lett. 111, 252402 (2017).
  88. C. Ulrich, G. Khaliullin, M. Guennou, H. Roth, T. Lorenz, and B. Keimer, Spin-orbital excitation continuum and anomalous electron-phonon interaction in the Mott insulator LaTiO3, Phys. Rev. Lett. 115, 156403 (2015).
  89. P. A. Sharma, J. S. Ahn, N. Hur, S. Park, S. B. Kim, S. Lee, J.-G. Park, S. Guha, and S.-W. Cheong, Thermal conductivity of geometrically frustrated, ferroelectric YMnO3: Extraordinary spin-phonon interactions, Phys. Rev. Lett. 93, 177202 (2004).
  90. D. Bansal, J. L. Niedziela, A. F. May, A. Said, G. Ehlers, D. L. Abernathy, A. Huq, M. Kirkham, H. Zhou, and O. Delaire, Lattice dynamics and thermal transport in multiferroic CuCrO2, Phys. Rev. B 95, 054306 (2017).
  91. M. Testa-Anta, J. N. Majcherkiewicz, K. Xu, A. R. Goñi, and V. Salgueiriño, Room temperature spin-phonon coupling in Cr2O3 nanocrystals, Adv. Funct. Mater. 33, 2301973 (2023).

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Phys. Rev. Research 7, 043189– Published 20 November, 2025
  • Received 14 May 2025
  • Accepted 10 October 2025
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