Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3

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.

doi:10.1073/pnas.1424431112

Title: 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:

Cheng, Jinguang ^[1]; Kweon, K. E. ^[2]; Larregola, S. A. ^[3]; Ding, Yang ^[4]; Shirako, Y. ^[3]; Marshall, L. G. ^[5]; Li, Z. -Y. ^[3]; Li, X. ^[3]; dos Santos, António M. ^[6]; Suchomel, M. R. ^[4]; Matsubayashi, K. ^[7]; Uwatoko, Y. ^[7]; Hwang, G. S. ^[2]; Goodenough, John B. ^[3]; Zhou, J. -S. ^[3]

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:: Mon Jan 26 00:00:00 EST 2015

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.

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                    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

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                    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.

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@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}

}

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Title: Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO 3

Abstract

Citation Formats

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Large volume collapse observed in the phase transition in cubic PbCrO3 perovskite journal, July 2010

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Structure, microstructure and magnetic properties of Sr1−xCaxCrO3 (0⩽x⩽1) journal, April 2008

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Title: Charge disproportionation and the pressure-induced insulator–metal transition in cubic perovskite PbCrO ₃

Prediction of the crystal structures of perovskites using the software program SPuDS
journal, November 2001

Large volume collapse observed in the phase transition in cubic PbCrO3 perovskite
journal, July 2010

Magnetic order, transport and infrared optical properties in the $A$ CrO $_{3}$ system ( $A$ $=$ Ca, Sr, and Pb)
journal, September 2011

Orbital ordering, ferroelasticity, and the large pressure-induced volume collapse in PbCrO $_{3}$
journal, May 2011

Determination of Valence States of Chromium in Calcium Chromates by Using X-ray Absorption Near-Edge Structure (XANES) Spectroscopy
journal, January 1998

First-principles study of pressure-induced phase transition and electronic property of PbCrO ₃
journal, January 2012

On the structure and microstructure of “PbCrO3”
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Structure, microstructure and magnetic properties of Sr1−xCaxCrO3 (0⩽x⩽1)
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Anomalous Electronic State in ${CaCrO}_{3}$ and ${SrCrO}_{3}$
journal, February 2006

The impact of crystal symmetry on the electronic structure and functional properties of complex lanthanum chromium oxides
journal, January 2013

Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides
journal, September 1976

The influence of coordination geometry and valency on the K-edge absorption near edge spectra of selected chromium compounds
journal, May 2004

Intrinsic structural distortion and superexchange interaction in the orthorhombic rare-earth perovskites $R {CrO}_{3}$
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The mystery of abnormally large volume of PbCrO3 with a structurally consistent Hubbard U from first-principles
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