Towards cubic symmetry for Ir4+: Structure and magnetism of the antifluorite K2IrBr6

Khan, Nazir; Prishchenko, Danil; Upton, Mary H.; Mazurenko, Vladimir G.; Tsirlin, Alexander A.

doi:10.1103/physrevb.103.125158

Towards cubic symmetry for ${Ir}^{4 +}$ : Structure and magnetism of the antifluorite $K_{2} {IrBr}_{6}$

Journal Article · Mon Mar 29 00:00:00 EDT 2021 · Physical Review B

DOI:https://doi.org/10.1103/physrevb.103.125158· OSTI ID:1774495

Khan, Nazir ^[1]; ^[2]; Upton, Mary H. ^[3]; ^[2]; ^[4]

Univ. of Augsburg (Germany)
Ural Federal Univ., Ekaterinburg (Russian Federation)
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Univ. of Augsburg (Germany); Ural Federal Univ., Ekaterinburg (Russian Federation)

Here, crystal structure, electronic state of ${Ir}^{4 +}$ , and magnetic properties of the antifluorite compound $K_{2} {IrBr}_{6}$ are studied using high-resolution synchrotron x-ray diffraction, resonant inelastic x-ray scattering (RIXS), thermodynamic and transport measurements, and ab initio calculations. The crystal symmetry is reduced from cubic at room temperature to tetragonal below 170 K and eventually to monoclinic below 122 K. These changes are tracked by the evolution of the noncubic crystal-field splitting $Δ$ measured by RIXS. Nonmonotonic changes in $Δ$ are ascribed to the competing effects of the tilt, rotation, and deformation of the ${IrBr}_{6}$ octahedra as well as tetragonal strain on the electronic levels of ${Ir}^{4 +}$ . The Néel temperature of $T_{N} = 11.9$ K exceeds that of the isostructural $K_{2} {IrCl}_{6}$ , and the magnitude of frustration on the fcc spin lattice decreases. We argue that the replacement of Cl by Br weakens electronic correlations and enhances magnetic couplings.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division; Ministry of Science and Higher Education of the Russian Federation

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1774495

Journal Information:: Physical Review B, Journal Name: Physical Review B Journal Issue: 12 Vol. 103; ISSN 2469-9950

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

References (47)

Na ₄ IrO ₄ : Square-Planar Coordination of a Transition Metal in d ⁵ Configuration due to Weak On-Site Coulomb Interactions Kanungo, Sudipta; Yan, Binghai; Merz, Patrick Angewandte Chemie International Edition, Vol. 54, Issue 18 https://doi.org/10.1002/anie.201411959	journal	March 2015
Neutron Powder Diffraction Study of the Crystal Structures of Sr2RuO4 and Sr2IrO4 at Room Temperature and at 10 K Huang, Q.; Soubeyroux, J. L.; Chmaissem, O. Journal of Solid State Chemistry, Vol. 112, Issue 2 https://doi.org/10.1006/jssc.1994.1316	journal	October 1994
Influence of d-electron configuration on phase transitions in A2MX6 (Hexahalometallates IV) Rössler, K.; Winter, J. Chemical Physics Letters, Vol. 46, Issue 3 https://doi.org/10.1016/0009-2614(77)80653-2	journal	March 1977
Crystal structure and phase transition of Rb2TeI6 Abriel, W. Materials Research Bulletin, Vol. 17, Issue 10 https://doi.org/10.1016/0025-5408(82)90171-4	journal	October 1982
Polymorphism and phase transitions of K2TeBr6: A single crystal investigation of the high temperature phases (383–463 K) Abriel, W. Materials Research Bulletin, Vol. 19, Issue 3 https://doi.org/10.1016/0025-5408(84)90172-7	journal	March 1984
Soft rotary mode and structural phase transitions in K2ReCl6 Lynn, J. W.; Patterson, H. H.; Shirane, G. Solid State Communications, Vol. 27, Issue 9 https://doi.org/10.1016/0038-1098(78)90192-8	journal	September 1978
Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set Kresse, G.; Furthmüller, J. Computational Materials Science, Vol. 6, Issue 1, p. 15-50 https://doi.org/10.1016/0927-0256(96)00008-0	journal	July 1996
First principles phonon calculations in materials science Togo, Atsushi; Tanaka, Isao Scripta Materialia, Vol. 108 https://doi.org/10.1016/j.scriptamat.2015.07.021	journal	November 2015
Diamagnetic Corrections and Pascal's Constants Bain, Gordon A.; Berry, John F. Journal of Chemical Education, Vol. 85, Issue 4 https://doi.org/10.1021/ed085p532	journal	April 2008
Orbital reconstruction in nonpolar tetravalent transition-metal oxide layers Bogdanov, Nikolay A.; Katukuri, Vamshi M.; Romhányi, Judit Nature Communications, Vol. 6, Issue 1 https://doi.org/10.1038/ncomms8306	journal	June 2015
Phase transition at 434 K, independent strain coupling in second transition at 400 K, and thermal expansivity in ferroelastic K ₂ TeBr ₆ Abrahams, S. C.; Ihringer, J.; Marsh, P. The Journal of Chemical Physics, Vol. 81, Issue 4 https://doi.org/10.1063/1.447832	journal	August 1984
The world’s smallest capacitive dilatometer, for high-resolution thermal expansion and magnetostriction in high magnetic fields Küchler, R.; Wörl, A.; Gegenwart, P. Review of Scientific Instruments, Vol. 88, Issue 8 https://doi.org/10.1063/1.4997073	journal	August 2017
Structural phase transitions I. Landau theory Cowley, R. A. Advances in Physics, Vol. 29, Issue 1 https://doi.org/10.1080/00018738000101346	journal	February 1980
Models and materials for generalized Kitaev magnetism Winter, Stephen M.; Tsirlin, Alexander A.; Daghofer, Maria Journal of Physics: Condensed Matter, Vol. 29, Issue 49 https://doi.org/10.1088/1361-648X/aa8cf5	journal	November 2017
The challenge of spin–orbit-tuned ground states in iridates: a key issues review Cao, Gang; Schlottmann, Pedro Reports on Progress in Physics, Vol. 81, Issue 4 https://doi.org/10.1088/1361-6633/aaa979	journal	February 2018
Antiferromagnetism in the face-centred cubic lattice by a spin-wave method Lines, M. E. Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, Vol. 271, Issue 1344, p. 105-119 https://doi.org/10.1098/rspa.1963.0007	journal	January 1963
A Spin-Wave Theory of Anisotropic Antiferromagnetica Haar, D. T.; Lines, M. E. Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 255, Issue 1049 https://doi.org/10.1098/rsta.1962.0008	journal	August 1962
Spin-orbit entangled j = 1 2 moments in Ba 2 CeIrO 6 : A frustrated fcc quantum magnet Revelli, A.; Loo, C. C.; Kiese, D. Physical Review B, Vol. 100, Issue 8 https://doi.org/10.1103/PhysRevB.100.085139	journal	August 2019
Quantum versus thermal fluctuations in the fcc antiferromagnet: Alternative routes to order by disorder Schick, R.; Ziman, T.; Zhitomirsky, M. E. Physical Review B, Vol. 102, Issue 22 https://doi.org/10.1103/PhysRevB.102.220405	journal	December 2020
Thermodynamical properties of K 2 Os Cl 6 and K 2 Re Cl 6 at low temperatures and near their structural phase transitions Novotny, Vladimir; Martin, Carlos A.; Armstrong, Robin L. Physical Review B, Vol. 15, Issue 1 https://doi.org/10.1103/PhysRevB.15.382	journal	January 1977
Thermal-expansion study of the displacive phase transitions in K 2 Re Cl 6 and K 2 Os Cl 6 Willemsen, Herman W.; Martin, Carlos A.; Meincke, Peter P. M. Physical Review B, Vol. 16, Issue 5 https://doi.org/10.1103/PhysRevB.16.2283	journal	September 1977
Ferrorotative transition in the antifluorite crystal K 2 Os Cl 6 Armstrong, Robin L.; Mintz, David; Powell, Brian M. Physical Review B, Vol. 17, Issue 3 https://doi.org/10.1103/PhysRevB.17.1260	journal	February 1978
Soft rotary mode in the antifluorite crystal K 2 OsC 1 6 Mintz, David; Armstrong, Robin L.; Powell, Brian M. Physical Review B, Vol. 19, Issue 1 https://doi.org/10.1103/PhysRevB.19.448	journal	January 1979
Lattice dynamics and phase transitions in antifluorite crystals: K 2 Os Cl 6 Sutton, Mark; Armstrong, Robin L.; Powell, Brian M. Physical Review B, Vol. 27, Issue 1 https://doi.org/10.1103/PhysRevB.27.380	journal	January 1983
Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Kresse, G.; Furthmüller, J. Physical Review B, Vol. 54, Issue 16, p. 11169-11186 https://doi.org/10.1103/PhysRevB.54.11169	journal	October 1996
Full-potential nonorthogonal local-orbital minimum-basis band-structure scheme Koepernik, Klaus; Eschrig, Helmut Physical Review B, Vol. 59, Issue 3 https://doi.org/10.1103/PhysRevB.59.1743	journal	January 1999
Softening of the Rotary Lattice Mode in K 2 Pt Br 6 as Detected by Nuclear Quadrupole Resonance Van Driel, Henry M.; Wiszniewska, Maria; Moores, B. Michael Physical Review B, Vol. 6, Issue 4 https://doi.org/10.1103/PhysRevB.6.1596	journal	August 1972
Exploring the spin- 1 2 frustrated square lattice model with high-field magnetization studies Tsirlin, Alexander A.; Schmidt, Burkhard; Skourski, Yurii Physical Review B, Vol. 80, Issue 13 https://doi.org/10.1103/PhysRevB.80.132407	journal	October 2009
Magnetism and electronic structure of La 2 ZnIrO 6 and La 2 MgIrO 6 : Candidate J eff = 1 2 Mott insulators Cao, Guixin; Subedi, Alaska; Calder, S. Physical Review B, Vol. 87, Issue 15 https://doi.org/10.1103/PhysRevB.87.155136	journal	April 2013
Challenges in design of Kitaev materials: Magnetic interactions from competing energy scales Winter, Stephen M.; Li, Ying; Jeschke, Harald O. Physical Review B, Vol. 93, Issue 21 https://doi.org/10.1103/PhysRevB.93.214431	journal	June 2016
Possibility to realize spin-orbit-induced correlated physics in iridium fluorides Rossi, M.; Retegan, M.; Giacobbe, C. Physical Review B, Vol. 95, Issue 23 https://doi.org/10.1103/PhysRevB.95.235161	journal	June 2017
Role of square planar coordination in the magnetic properties of Na 4 IrO 4 Ming, Xing; Autieri, Carmine; Yamauchi, Kunihiko Physical Review B, Vol. 96, Issue 20 https://doi.org/10.1103/PhysRevB.96.205158	journal	November 2017
Thermodynamic evidence of fractionalized excitations in α − RuC l 3 Widmann, S.; Tsurkan, V.; Prishchenko, D. A. Physical Review B, Vol. 99, Issue 9 https://doi.org/10.1103/PhysRevB.99.094415	journal	March 2019
Revisiting the Kitaev material candidacy of Ir 4 + double perovskite iridates Aczel, A. A.; Clancy, J. P.; Chen, Q. Physical Review B, Vol. 99, Issue 13 https://doi.org/10.1103/PhysRevB.99.134417	journal	April 2019
Cubic symmetry and magnetic frustration on the fcc spin lattice in K 2 IrCl 6 Khan, Nazir; Prishchenko, Danil; Skourski, Yurii Physical Review B, Vol. 99, Issue 14 https://doi.org/10.1103/PhysRevB.99.144425	journal	April 2019
Crystal-Field Splitting and Correlation Effect on the Electronic Structure of A 2 IrO 3 Gretarsson, H.; Clancy, J. P.; Liu, X. Physical Review Letters, Vol. 110, Issue 7 https://doi.org/10.1103/PhysRevLett.110.076402	journal	February 2013
Generic Spin Model for the Honeycomb Iridates beyond the Kitaev Limit Rau, Jeffrey G.; Lee, Eric Kin-Ho; Kee, Hae-Young Physical Review Letters, Vol. 112, Issue 7 https://doi.org/10.1103/PhysRevLett.112.077204	journal	February 2014
CaIrO 3 : A Spin-Orbit Mott Insulator Beyond the j eff = 1 / 2 Ground State Sala, M. Moretti; Ohgushi, K.; Al-Zein, A. Physical Review Letters, Vol. 112, Issue 17 https://doi.org/10.1103/PhysRevLett.112.176402	journal	April 2014
Covalency Effects in the Magnetic Form Factor of Ir in K 2 Ir Cl 6 Lynn, J. W.; Shirane, G.; Blume, M. Physical Review Letters, Vol. 37, Issue 3 https://doi.org/10.1103/PhysRevLett.37.154	journal	July 1976
Generalized Gradient Approximation Made Simple Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868 https://doi.org/10.1103/PhysRevLett.77.3865	journal	October 1996
Anisotropic temperature-field phase diagram of single crystalline β − Li 2 IrO 3 : Magnetization, specific heat, and Li 7 NMR study Majumder, M.; Freund, F.; Dey, T. Physical Review Materials, Vol. 3, Issue 7 https://doi.org/10.1103/PhysRevMaterials.3.074408	journal	July 2019
Structural, electronic, and magnetic properties of nearly ideal J e f f = 1 2 iridium halides Reig-i-Plessis, D.; Johnson, T. A.; Lu, K. Physical Review Materials, Vol. 4, Issue 12 https://doi.org/10.1103/PhysRevMaterials.4.124407	journal	December 2020
Crystal structure of post-perovskite-type CaIrO ₃ reinvestigated: new insights into atomic thermal vibration behaviors Nakatsuka, Akihiko; Sugiyama, Kazumasa; Yoneda, Akira Acta Crystallographica Section E Crystallographic Communications, Vol. 71, Issue 9 https://doi.org/10.1107/S2056989015015649	journal	August 2015
Correlated Quantum Phenomena in the Strong Spin-Orbit Regime Witczak-Krempa, William; Chen, Gang; Kim, Yong Baek Annual Review of Condensed Matter Physics, Vol. 5, Issue 1 https://doi.org/10.1146/annurev-conmatphys-020911-125138	journal	March 2014
Spin-Orbit Physics Giving Rise to Novel Phases in Correlated Systems: Iridates and Related Materials Rau, Jeffrey G.; Lee, Eric Kin-Ho; Kee, Hae-Young Annual Review of Condensed Matter Physics, Vol. 7, Issue 1 https://doi.org/10.1146/annurev-conmatphys-031115-011319	journal	March 2016
Square Lattice Iridates Bertinshaw, Joel; Kim, Y. K.; Khaliullin, Giniyat Annual Review of Condensed Matter Physics, Vol. 10, Issue 1 https://doi.org/10.1146/annurev-conmatphys-031218-013113	journal	March 2019
Crystallographic Computing System JANA2006: General features Petříček, Václav; Dušek, Michal; Palatinus, Lukáš Zeitschrift für Kristallographie - Crystalline Materials, Vol. 229, Issue 5 https://doi.org/10.1515/zkri-2014-1737	journal	January 2014

Similar Records

Structural and electronic properties of the first iridium containing mixed B-site spinel oxide:

Cu [{Ir}_{1.5} {Cu}_{0.5}] O_{4}

Journal Article · Mon Sep 27 00:00:00 EDT 2021 · Physical Review Materials · OSTI ID:1839091

Quasi-one-dimensional uniform spin-

\frac{1}{2}

Heisenberg antiferromagnet

{KNaCuP}_{2} O_{7}

probed by

{}^{31}P

and

{}^{23}{Na}

NMR

Journal Article · Mon Jun 14 00:00:00 EDT 2021 · Physical Review B · OSTI ID:1798870

Spin correlation in trigonal

{EuMn}_{2} {As}_{2}

Journal Article · Sun Feb 24 23:00:00 EST 2019 · Physical Review B · OSTI ID:1594103

Related Subjects

75 CONDENSED MATTER PHYSICS
SUPERCONDUCTIVITY AND SUPERFLUIDITY
Mott insulators
antiferromagnets
crystal growth
crystal structures
dc susceptibility measurements
density functional calculations
exchange interaction
face-centered cubicionic solids
first-principles calculations
resistivity measurements
resonant inelastic x-ray scattering
specific heat measurements
spin-orbit coupling
structural phase transition
thermodilatometry
x-ray powder diffraction

Towards cubic symmetry for Ir4+ : Structure and magnetism of the antifluorite K2IrBr6

Citation Formats

References (47)

Similar Records

Related Subjects

Towards cubic symmetry for ${Ir}^{4 +}$ : Structure and magnetism of the antifluorite $K_{2} {IrBr}_{6}$