Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3
Abstract
The perovskite PbCrO3 is an antiferromagnetic insulator. But, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. Our report shows a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. Furthermore, we argue that a charge disproportionation 3Cr4+ → 2Cr3+ + Cr6+ in association with the 6s-p hybridization on the Pb2+ is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT + U) calculations.
- Authors:
-
- Materials Science and Engineering Program and Texas Materials Institute, University of Texas at Austin, Austin, TX 78712,, Beijing National Laboratory for Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China,, Institute for Solid State Physics, University of Tokyo, Kashiwa 277-8581, Japan,
- Chemical Engineering and Texas Materials Institute, University of Texas at Austin, Austin, TX 78712,
- Materials Science and Engineering Program and Texas Materials Institute, University of Texas at Austin, Austin, TX 78712,
- Advanced Photo Source, Argonne National Laboratory, Argonne, IL 60439,
- Materials Science and Engineering Program and Texas Materials Institute, University of Texas at Austin, Austin, TX 78712,, Department of Chemical Engineering, Northeastern University, Boston, MA 02115, and
- Quantum Condensed Matter Division, Oak Ridge National Laboratory, Oak Ridge, TN 37831
- Institute for Solid State Physics, University of Tokyo, Kashiwa 277-8581, Japan,
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1235506
- Alternate Identifier(s):
- OSTI ID: 1334440
- Grant/Contract Number:
- AC02-06CH11357; AC05-00OR22725
- Resource Type:
- Published Article
- Journal Name:
- Proceedings of the National Academy of Sciences of the United States of America
- Additional Journal Information:
- Journal Name: Proceedings of the National Academy of Sciences of the United States of America Journal Volume: 112 Journal Issue: 6; Journal ID: ISSN 0027-8424
- Publisher:
- Proceedings of the National Academy of Sciences
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; high pressure; perovskite; insulator-metal transition; charge disproportionation; LARGE-VOLUME; MICROSTRUCTURE; SPECTROSCOPY; CHROMIUM; CRYSTAL
Citation Formats
Cheng, Jinguang, Kweon, K. E., Larregola, S. A., Ding, Yang, Shirako, Y., Marshall, L. G., Li, Z. -Y., Li, X., dos Santos, António M., Suchomel, M. R., Matsubayashi, K., Uwatoko, Y., Hwang, G. S., Goodenough, John B., and Zhou, J. -S. Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3. United States: N. p., 2015.
Web. doi:10.1073/pnas.1424431112.
Cheng, Jinguang, Kweon, K. E., Larregola, S. A., Ding, Yang, Shirako, Y., Marshall, L. G., Li, Z. -Y., Li, X., dos Santos, António M., Suchomel, M. R., Matsubayashi, K., Uwatoko, Y., Hwang, G. S., Goodenough, John B., & Zhou, J. -S. Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3. United States. https://doi.org/10.1073/pnas.1424431112
Cheng, Jinguang, Kweon, K. E., Larregola, S. A., Ding, Yang, Shirako, Y., Marshall, L. G., Li, Z. -Y., Li, X., dos Santos, António M., Suchomel, M. R., Matsubayashi, K., Uwatoko, Y., Hwang, G. S., Goodenough, John B., and Zhou, J. -S. Mon .
"Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3". United States. https://doi.org/10.1073/pnas.1424431112.
@article{osti_1235506,
title = {Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3},
author = {Cheng, Jinguang and Kweon, K. E. and Larregola, S. A. and Ding, Yang and Shirako, Y. and Marshall, L. G. and Li, Z. -Y. and Li, X. and dos Santos, António M. and Suchomel, M. R. and Matsubayashi, K. and Uwatoko, Y. and Hwang, G. S. and Goodenough, John B. and Zhou, J. -S.},
abstractNote = {The perovskite PbCrO3 is an antiferromagnetic insulator. But, the fundamental interactions leading to the insulating state in this single-valent perovskite are unclear. Moreover, the origin of the unprecedented volume drop observed at a modest pressure of P = 1.6 GPa remains an outstanding problem. Our report shows a variety of in situ pressure measurements including electron transport properties, X-ray absorption spectrum, and crystal structure study by X-ray and neutron diffraction. These studies reveal key information leading to the elucidation of the physics behind the insulating state and the pressure-induced transition. Furthermore, we argue that a charge disproportionation 3Cr4+ → 2Cr3+ + Cr6+ in association with the 6s-p hybridization on the Pb2+ is responsible for the insulating ground state of PbCrO3 at ambient pressure and the charge disproportionation phase is suppressed under pressure to give rise to a metallic phase at high pressure. The model is well supported by density function theory plus the correlation energy U (DFT + U) calculations.},
doi = {10.1073/pnas.1424431112},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 6,
volume = 112,
place = {United States},
year = {Mon Jan 26 00:00:00 EST 2015},
month = {Mon Jan 26 00:00:00 EST 2015}
}
https://doi.org/10.1073/pnas.1424431112
Web of Science
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