TY - JOUR
T1 - Intermetallic Charge Transfer in V-Substituted PbCrO3
AU - Ogata, Takahiro
AU - Sakai, Yuki
AU - Nishikubo, Takumi
AU - Mizokawa, Takashi
AU - Mizumaki, Masaichiro
AU - Lee, Koomok
AU - Liu, Qiumin
AU - Azuma, Masaki
N1 - Funding Information:
This work was partially supported by JSPS KAKENHI JP18H05208 and JP19H05625 and the Kanagawa Institute of Industrial Science and Technology (KISTEC). The synchrotron radiation experiments were performed at SPring-8 with the approval of the Japan Synchrotron Radiation Research Institute (2018A1667 and 2018B1672).
Publisher Copyright:
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PY - 2021/7/5
Y1 - 2021/7/5
N2 - PbCrO3 features an unusual charge distribution Pb0.52+Pb0.54+Cr3+O3 with Pb charge disproportionation at ambient pressure. A charge transfer between Pb and Cr is induced by the application of pressure resulting in Pb2+Cr4+O3 charge distribution and a large volume collapse. Here, structural and charge distribution changes in PbCr1-xVxO3 are investigated. Despite a cubic crystal structure in 0 ≤ x ≤ 0.60, discontinuous reduction in the unit cell volume was observed between x = 0.35 and 0.40. Hard X-ray photoemission spectroscopy confirmed the change in Pb charge state from the coexisting Pb2+ and Pb4+ at x = 0.35 to single Pb2+ at x = 0.40. This indicates that V substitution stabilizes the high pressure cubic Pb2+Cr4+O3-Type phase. With further increase in the V substitution, the PbVO3-Type polar tetragonal phase appeared at x = 0.80.
AB - PbCrO3 features an unusual charge distribution Pb0.52+Pb0.54+Cr3+O3 with Pb charge disproportionation at ambient pressure. A charge transfer between Pb and Cr is induced by the application of pressure resulting in Pb2+Cr4+O3 charge distribution and a large volume collapse. Here, structural and charge distribution changes in PbCr1-xVxO3 are investigated. Despite a cubic crystal structure in 0 ≤ x ≤ 0.60, discontinuous reduction in the unit cell volume was observed between x = 0.35 and 0.40. Hard X-ray photoemission spectroscopy confirmed the change in Pb charge state from the coexisting Pb2+ and Pb4+ at x = 0.35 to single Pb2+ at x = 0.40. This indicates that V substitution stabilizes the high pressure cubic Pb2+Cr4+O3-Type phase. With further increase in the V substitution, the PbVO3-Type polar tetragonal phase appeared at x = 0.80.
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U2 - 10.1021/acs.inorgchem.1c00460
DO - 10.1021/acs.inorgchem.1c00460
M3 - Article
C2 - 33905652
AN - SCOPUS:85106527802
SN - 0020-1669
VL - 60
SP - 9427
EP - 9431
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 13
ER -