Tetrahedral coordination and low-spin configuration in a 5d oxide

doi:10.1103/PhysRevMaterials.3.063607

This content will become publicly available on June 17, 2020

Title: Tetrahedral coordination and low-spin configuration in a $5 d$ oxide

Abstract

Spin state plays an essential role in a plethora of physical, biological, and geological phenomena. In octahedral coordination, spin state of $3 d$ transition metals can be high spin or low spin, and can be tuned with external stimuli. In a tetrahedral coordination environment, with the smaller crystal field splitting energy, only high spin is considered possible for oxides. In this work, we report on the realization of low spin state in tetrahedral coordination in a novel oxide, Sr ₉Ir ₃O ₁₇. The low spin configuration was confirmed with density functional theory (DFT) calculations, including the effect of spin-orbit coupling (SOC), electron-electron repulsion ( U), magnetic data, and crystal chemical consideration. This exotic electronic configuration was realized with the confluence of extended $5 d$ orbitals, short bond lengths, and an electron count maximizing the crystal field stabilization energy. The discovery of low spin state for a tetrahedral environment provides a novel platform for spin state manipulation in solid state materials.

Authors:

Zhao, Qingbiao ^[1]; Sim, Jae-Hoon ^[2]; Zhang, Zaiyong ^[3]; Su, Haifeng ^[4]; Han, Fei ^[5]; Zhang, Qiang ^[6]; Tian, B. ^[1]; Xu, Quan ^[7]; Han, Myung Joon ^[2]; Duan, Chun-Gang ^[1]; Mitchell, J. F. ^[5]

East China Normal Univ. (ECNU), Shanghai (China)
Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
Chinese Academy of Sciences (CAS), Shanghai (China)
Chinese Academy of Sciences (CAS), Chongqing (China)
Argonne National Lab. (ANL), Lemont, IL (United States)
Washington State Univ., Pullman, WA (United States)
China Univ. of Petroleum, Beijing (China)

Publication Date:: 2019-06-17

Research Org.:: Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; National Research Foundation of Korea (NRF); National Key Project for Basic Research of China

OSTI Identifier:: 1530383

Grant/Contract Number:: AC02-06CH11357

Resource Type:: Accepted Manuscript

Journal Name:: Physical Review Materials

Additional Journal Information:: Journal Volume: 3; Journal Issue: 6; Journal ID: ISSN 2475-9953

Publisher:: American Physical Society (APS)

Country of Publication:: United States

Language:: English

Subject:: 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY

Citation Formats


                    Zhao, Qingbiao, Sim, Jae-Hoon, Zhang, Zaiyong, Su, Haifeng, Han, Fei, Zhang, Qiang, Tian, B., Xu, Quan, Han, Myung Joon, Duan, Chun-Gang, and Mitchell, J. F. Tetrahedral coordination and low-spin configuration in a 5d oxide.  United States: N. p., 2019. 
        Web.  doi:10.1103/PhysRevMaterials.3.063607.

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                    Zhao, Qingbiao, Sim, Jae-Hoon, Zhang, Zaiyong, Su, Haifeng, Han, Fei, Zhang, Qiang, Tian, B., Xu, Quan, Han, Myung Joon, Duan, Chun-Gang, & Mitchell, J. F. Tetrahedral coordination and low-spin configuration in a 5d oxide.  United States.  doi:10.1103/PhysRevMaterials.3.063607.

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                    Zhao, Qingbiao, Sim, Jae-Hoon, Zhang, Zaiyong, Su, Haifeng, Han, Fei, Zhang, Qiang, Tian, B., Xu, Quan, Han, Myung Joon, Duan, Chun-Gang, and Mitchell, J. F. Mon .  
        "Tetrahedral coordination and low-spin configuration in a 5d oxide".  United States.  doi:10.1103/PhysRevMaterials.3.063607.

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@article{osti_1530383,

  title        = {Tetrahedral coordination and low-spin configuration in a 5d oxide},

  author       = {Zhao, Qingbiao and Sim, Jae-Hoon and Zhang, Zaiyong and Su, Haifeng and Han, Fei and Zhang, Qiang and Tian, B. and Xu, Quan and Han, Myung Joon and Duan, Chun-Gang and Mitchell, J. F.},

  abstractNote = {Spin state plays an essential role in a plethora of physical, biological, and geological phenomena. In octahedral coordination, spin state of 3d transition metals can be high spin or low spin, and can be tuned with external stimuli. In a tetrahedral coordination environment, with the smaller crystal field splitting energy, only high spin is considered possible for oxides. In this work, we report on the realization of low spin state in tetrahedral coordination in a novel oxide, Sr9Ir3O17. The low spin configuration was confirmed with density functional theory (DFT) calculations, including the effect of spin-orbit coupling (SOC), electron-electron repulsion (U), magnetic data, and crystal chemical consideration. This exotic electronic configuration was realized with the confluence of extended 5d orbitals, short bond lengths, and an electron count maximizing the crystal field stabilization energy. The discovery of low spin state for a tetrahedral environment provides a novel platform for spin state manipulation in solid state materials.},

  doi          = {10.1103/PhysRevMaterials.3.063607},

  journal      = {Physical Review Materials},

  number       = 6,

  volume       = 3,

  place        = {United States},

  year         = {2019},

  month        = {6}

}

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Works referenced in this record:

A short history of SHELX
journal, December 2007

Sheldrick, George M.
Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
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DOI: 10.1103/PhysRevLett.77.3865

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
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Dudarev, S. L.; Botton, G. A.; Savrasov, S. Y.
Physical Review B, Vol. 57, Issue 3, p. 1505-1509
DOI: 10.1103/PhysRevB.57.1505

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

Shannon, R. D.
Acta Crystallographica Section A, Vol. 32, Issue 5, p. 751-767
DOI: 10.1107/S0567739476001551

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Similar Records

This content will become publicly available on June 17, 2020

Title: Tetrahedral coordination and low-spin configuration in a 5 d oxide

Abstract

Citation Formats

A short history of SHELX journal, December 2007

Generalized Gradient Approximation Made Simple journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study journal, January 1998

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

Title: Tetrahedral coordination and low-spin configuration in a $5 d$ oxide

A short history of SHELX
journal, December 2007

Generalized Gradient Approximation Made Simple
journal, October 1996

Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study
journal, January 1998

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