skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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]
  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.
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.
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. https://www.osti.gov/servlets/purl/1530383.
@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}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Spin transition of iron in magnesiowüstite in the Earth's lower mantle
journal, July 2005

  • Lin, Jung-Fu; Struzhkin, Viktor V.; Jacobsen, Steven D.
  • Nature, Vol. 436, Issue 7049
  • DOI: 10.1038/nature03825

On the State of the Iron and the Nature of the Ligand in Oxyhemoglobin
journal, December 1970

  • Wittenberg, J. B.; Wittenberg, B. A.; Peisach, J.
  • Proceedings of the National Academy of Sciences, Vol. 67, Issue 4
  • DOI: 10.1073/pnas.67.4.1846

Thermal, pressure and light switchable spin-crossover materials
journal, January 2005

  • Real, José Antonio; Gaspar, Ana Belén; Muñoz, M. Carmen
  • Dalton Transactions, Issue 12
  • DOI: 10.1039/b501491c

Low to High Spin-State Transition Induced by Charge Ordering in Antiferromagnetic YBaCo 2 O 5
journal, March 2000


Metal-insulator transition induced by a spin-state transition in TbBaCo 2 O 5 + δ ( δ = 0.5 )
journal, May 2000


Magnetoresistance of the spin-state-transition compound La 1 x Sr x CoO 3
journal, December 1996


Crystal Structure of the Transition‐Metal Molybdates and Tungstates. II. Diamagnetic Sc 2 (WO 4 ) 3
journal, October 1966

  • Abrahams, S. C.; Bernstein, J. L.
  • The Journal of Chemical Physics, Vol. 45, Issue 8
  • DOI: 10.1063/1.1728021

The crystal structure of KReO4
journal, May 1960


Synthesis and properties of alkali-metal tetraoxo-osmate(VII) compounds
journal, January 1985

  • Levason, William; Tajik, Mahmoud; Webster, Michael
  • Journal of the Chemical Society, Dalton Transactions, Issue 8
  • DOI: 10.1039/dt9850001735

Identification of an iridium-containing compound with a formal oxidation state of IX
journal, October 2014

  • Wang, Guanjun; Zhou, Mingfei; Goettel, James T.
  • Nature, Vol. 514, Issue 7523
  • DOI: 10.1038/nature13795

Electrocatalytic Oxygen Evolution Reaction (OER) on Ru, Ir, and Pt Catalysts: A Comparative Study of Nanoparticles and Bulk Materials
journal, July 2012

  • Reier, Tobias; Oezaslan, Mehtap; Strasser, Peter
  • ACS Catalysis, Vol. 2, Issue 8
  • DOI: 10.1021/cs3003098

Nanosized IrO x -Ir Catalyst with Relevant Activity for Anodes of Proton Exchange Membrane Electrolysis Produced by a Cost-Effective Procedure
journal, November 2015

  • Lettenmeier, Philipp; Wang, Li; Golla-Schindler, Ute
  • Angewandte Chemie International Edition, Vol. 55, Issue 2
  • DOI: 10.1002/anie.201507626

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
  • DOI: 10.1107/S0108767307043930

ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005


Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure Database
journal, August 1985

  • Brown, I. D.; Altermatt, D.
  • Acta Crystallographica Section B Structural Science, Vol. 41, Issue 4
  • DOI: 10.1107/S0108768185002063

Bond-valence parameters for solids
journal, April 1991

  • Brese, N. E.; O'Keeffe, M.
  • Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2
  • DOI: 10.1107/S0108768190011041

Variationally optimized atomic orbitals for large-scale electronic structures
journal, April 2003


Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Spin-polarised relativistic exchange energies and potentials
journal, July 1983


O ( N ) LDA + U electronic structure calculation method based on the nonorthogonal pseudoatomic orbital basis
journal, January 2006


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

  • 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

Electronic structure and magnetic properties of iridate superlattice SrIrO 3 /SrTiO 3
journal, April 2014


Calculating branching ratio and spin-orbit coupling from first principles: A formalism and its application to iridates
journal, September 2016


Spin-orbital entangled molecular jeff states in lacunar spinel compounds
journal, June 2014

  • Kim, Heung-Sik; Im, Jino; Han, Myung Joon
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms4988

Novel J eff = 1 / 2 Mott State Induced by Relativistic Spin-Orbit Coupling in Sr 2 IrO 4
journal, August 2008


The Principles Determining the Structure of Complex Ionic Crystals
journal, April 1929

  • Pauling, Linus
  • Journal of the American Chemical Society, Vol. 51, Issue 4
  • DOI: 10.1021/ja01379a006

Purification and crystal growth of potassium perrhenate, KReO4
journal, March 1971


Synthesis and Crystal Structure of Potassium Osmate(VIII), K2OsO5
journal, February 2005

  • Mogare, Kailash M.; Klein, Wilhelm; Jansen, Martin
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 631, Issue 2-3
  • DOI: 10.1002/zaac.200400403

Hydrogeniridate(VI) Anion and the Geometries of Tetrahedral Oxo-anions
journal, May 2014

  • Weller, Mark T.; Galati, Rosa
  • Inorganic Chemistry, Vol. 53, Issue 11
  • DOI: 10.1021/ic500371n

Nd 2 K 2 IrO 7 and Sm 2 K 2 IrO 7 : Iridium(VI) Oxides Prepared under Ambient Pressure
journal, November 2008

  • Mugavero, Samuel J.; Smith, Mark D.; Yoon, Won-Sub
  • Angewandte Chemie International Edition, Vol. 48, Issue 1
  • DOI: 10.1002/anie.200804045

High Oxygen Pressure and the Preparation of New Iridium (VI) Oxides with Perovskite Structure: Sr2MIrO6 (M = Ca, Mg)
journal, March 1995

  • Jung, Duk-Young; Demazeau, Gérard
  • Journal of Solid State Chemistry, Vol. 115, Issue 2
  • DOI: 10.1006/jssc.1995.1158

Observation of the crystal-field splitting related to the Mn-3d bands in spinel-LiMn2O4 films by optical absorption
journal, December 2000

  • Kushida, K.; Kuriyama, K.
  • Applied Physics Letters, Vol. 77, Issue 25
  • DOI: 10.1063/1.1336552

Novel Magnetism of Ir 5 + ( 5 d 4 ) Ions in the Double Perovskite Sr 2 YIrO 6
journal, February 2014


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


Effect of Spin–Orbit Interaction on (4 d ) 3 - and (5 d ) 3 -Based Transition-Metal Oxides
journal, July 2013

  • Matsuura, Hiroyasu; Miyake, Kazumasa
  • Journal of the Physical Society of Japan, Vol. 82, Issue 7
  • DOI: 10.7566/JPSJ.82.073703