Tetrahedral coordination and low-spin configuration in a oxide
Abstract
Spin state plays an essential role in a plethora of physical, biological, and geological phenomena. In octahedral coordination, spin state of 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 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:
-
- 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:
- 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. https://doi.org/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. https://doi.org/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}
}
Web of Science
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
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
Thermal, pressure and light switchable spin-crossover materials
journal, January 2005
- Real, José Antonio; Gaspar, Ana Belén; Muñoz, M. Carmen
- Dalton Transactions, Issue 12
Low to High Spin-State Transition Induced by Charge Ordering in Antiferromagnetic
journal, March 2000
- Vogt, T.; Woodward, P. M.; Karen, P.
- Physical Review Letters, Vol. 84, Issue 13
Metal-insulator transition induced by a spin-state transition in
journal, May 2000
- Moritomo, Y.; Akimoto, T.; Takeo, M.
- Physical Review B, Vol. 61, Issue 20
Magnetoresistance of the spin-state-transition compound
journal, December 1996
- Mahendiran, R.; Raychaudhuri, A. K.
- Physical Review B, Vol. 54, Issue 22
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
The crystal structure of KReO4
journal, May 1960
- Morrow, J. C.
- Acta Crystallographica, Vol. 13, Issue 5
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
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
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
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
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
ATHENA , ARTEMIS , HEPHAESTUS : data analysis for X-ray absorption spectroscopy using IFEFFIT
journal, June 2005
- Ravel, B.; Newville, M.
- Journal of Synchrotron Radiation, Vol. 12, Issue 4
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
Bond-valence parameters for solids
journal, April 1991
- Brese, N. E.; O'Keeffe, M.
- Acta Crystallographica Section B Structural Science, Vol. 47, Issue 2
Variationally optimized atomic orbitals for large-scale electronic structures
journal, April 2003
- Ozaki, T.
- Physical Review B, Vol. 67, Issue 15
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
Spin-polarised relativistic exchange energies and potentials
journal, July 1983
- MacDonald, A. H.
- Journal of Physics C: Solid State Physics, Vol. 16, Issue 20
electronic structure calculation method based on the nonorthogonal pseudoatomic orbital basis
journal, January 2006
- Han, Myung Joon; Ozaki, Taisuke; Yu, Jaejun
- Physical Review B, Vol. 73, Issue 4
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
Electronic structure and magnetic properties of iridate superlattice SrIrO 3 /SrTiO 3
journal, April 2014
- Kim, K-H; Kim, H-S; Han, M. J.
- Journal of Physics: Condensed Matter, Vol. 26, Issue 18
Calculating branching ratio and spin-orbit coupling from first principles: A formalism and its application to iridates
journal, September 2016
- Sim, Jae-Hoon; Yoon, Hongkee; Park, Sang Hyeon
- Physical Review B, Vol. 94, Issue 11
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
Novel Mott State Induced by Relativistic Spin-Orbit Coupling in
journal, August 2008
- Kim, B. J.; Jin, Hosub; Moon, S. J.
- Physical Review Letters, Vol. 101, Issue 7
The Principles Determining the Structure of Complex Ionic Crystals
journal, April 1929
- Pauling, Linus
- Journal of the American Chemical Society, Vol. 51, Issue 4
Purification and crystal growth of potassium perrhenate, KReO4
journal, March 1971
- Plovnick, R. H.; Schmidt, G. E.
- Journal of Crystal Growth, Vol. 8, Issue 3
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
Hydrogeniridate(VI) Anion and the Geometries of Tetrahedral Oxo-anions
journal, May 2014
- Weller, Mark T.; Galati, Rosa
- Inorganic Chemistry, Vol. 53, Issue 11
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
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
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
Novel Magnetism of Ions in the Double Perovskite
journal, February 2014
- Cao, G.; Qi, T. F.; Li, L.
- Physical Review Letters, Vol. 112, Issue 5
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
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