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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, 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 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:
 [1];  [2];  [3];  [4];  [5];  [6];  [1];  [7];  [2];  [1];  [5]
+ Show Author Affiliations
  1. East China Normal Univ. (ECNU), Shanghai (China)
  2. Korea Advanced Inst. Science and Technology (KAIST), Daejeon (Korea, Republic of)
  3. Chinese Academy of Sciences (CAS), Shanghai (China)
  4. Chinese Academy of Sciences (CAS), Chongqing (China)
  5. Argonne National Lab. (ANL), Lemont, IL (United States)
  6. Washington State Univ., Pullman, WA (United States)
  7. China Univ. of Petroleum, Beijing (China)
Publication Date:
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; USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1530383
Alternate Identifier(s):
OSTI ID: 1546413
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. https://doi.org/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. https://doi.org/10.1103/PhysRevMaterials.3.063607. https://www.osti.gov/servlets/purl/1530383.
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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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https://doi.org/10.1103/PhysRevMaterials.3.063607
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