DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Local Moment Instability of Os in Honeycomb Li2.15Os0.85O3

Journal Article · · Scientific Reports
 [1];  [2]; ORCiD logo [1];  [3];  [3];  [4];  [5];  [2];  [1]
  1. Oregon State Univ., Corvallis, OR (United States)
  2. Univ. of California Santa Cruz, Santa Cruz, CA (United States)
  3. Univ. of California Davis, Davis, CA (United States)
  4. Univ. of Colorado, Denver, CO (United States)
  5. Argonne National Lab. (ANL), Argonne, IL (United States)

Compounds with honeycomb structures occupied by strong spin orbit coupled (SOC) moments are considered to be candidate Kitaev quantum spin liquids. Here we present the first example of Os on a honeycomb structure, Li2.15(3)Os0.85(3)O3 (C2/c, a = 5.09 Å, b = 8.81 Å, c = 9.83 Å, β = 99.3°). Neutron diffraction shows large site disorder in the honeycomb layer and X-ray absorption spectroscopy indicates a valence state of Os (4.7 ± 0.2), consistent with the nominal concentration. We observe a transport band gap of Δ = 243 ± 23 meV, a large van Vleck susceptibility, and an effective moment of 0.85 μB, much lower than expected from 70% Os(+5). No evidence of long range order is found above 0.10 K but a spin glass-like peak in ac-susceptibility is observed at 0.5 K. The specific heat displays an impurity spin contribution in addition to a power law ∝T(0.63±0.06). Applied density functional theory (DFT) leads to a reduced moment, suggesting incipient itineracy of the valence electrons, and finding evidence that Li over stoichiometry leads to Os(4+)–Os(5+) mixed valence. Lastly, this local picture is discussed in light of the site disorder and a possible underlying quantum spin liquid state.

Research Organization:
Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-06CH11357
OSTI ID:
1435605
Journal Information:
Scientific Reports, Vol. 8, Issue 1; ISSN 2045-2322
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 5 works
Citation information provided by
Web of Science

References (51)

Fragility of ferromagnetic double exchange interactions and pressure tuning of magnetism in 3 d − 5 d double perovskite Sr 2 FeOsO 6 journal June 2015
Generalized Gradient Approximation Made Simple journal October 1996
A General Recursion Method for Calculating Diffracted Intensities from Crystals Containing Planar Faults
  • Treacy, M. M. J.; Newsam, J. M.; Deem, M. W.
  • Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 433, Issue 1889 https://doi.org/10.1098/rspa.1991.0062
journal June 1991
The magnetic behavior of Li2MO3 (M=Mn, Ru and Ir) and Li2(Mn1−xRux)O3 journal February 2002
Anyons in an exactly solved model and beyond journal January 2006
Insulating nature of Na 2 IrO 3 : Mott-type or Slater-type journal May 2016
Strongly frustrated triangular spin lattice emerging from triplet dimer formation in honeycomb Li2IrO3 journal January 2016
Structure, and magnetic and electrochemical properties of layered oxides, Li2IrO3 journal February 2003
EXPGUI , a graphical user interface for GSAS journal April 2001
Neutron scattering in the proximate quantum spin liquid α-RuCl 3 journal June 2017
Hyperhoneycomb Iridate β − Li 2 IrO 3 as a Platform for Kitaev Magnetism journal February 2015
Zur Kenntnis der NaCl-Strukturfamilie: Neue Untersuchungen an Li2MnO3 journal April 1973
Lattice-tuned magnetism of Ru 4 + ( 4 d 4 ) ions in single crystals of the layered honeycomb ruthenates Li 2 RuO 3 and Na 2 RuO 3 journal October 2014
Relevance of the Heisenberg-Kitaev Model for the Honeycomb Lattice Iridates A 2 IrO 3 journal March 2012
First-Principles Study of the Magnetic Structure of Na 2 IrO 3 journal October 2015
Structural, magnetic, and electrical properties of Li 2 Ir 1 − x Ru x O 3 journal January 2014
Structure and bonding in Li2MoO3 and Li2−xMoO3 (0 ≤ x ≤ 1.7) journal September 1988
Electronic excitations in γ − Li 2 IrO 3 journal January 2017
Recent developments in the ABINIT software package journal August 2016
Electrochemical Investigations on the Effect of Mg-Substitution in Li 2 MnO 3 Cathode journal January 2017
Synthesis and characterization of O3-Na3LiFeSbO6: A new honeycomb ordered layered oxide journal February 2014
Local Probe for Spin-Orbit Interaction journal May 1988
Excitonic Magnetism in Van Vleck–type d 4 Mott Insulators journal November 2013
Orbital Magnetism and Spin-Orbit Effects in the Electronic Structure of BaIrO 3 journal November 2010
Origin of the insulating state in honeycomb iridates and rhodates journal July 2013
Structural and anisotropic thermal expansion correlation of Li 2 ZrO 3 at different temperatures journal September 2002
γ and β cerium: LDA + U calculations of ground-state parameters journal April 2008
ABINIT: First-principles approach to material and nanosystem properties journal December 2009
Antiferromagnetic Mott insulating state in single crystals of the honeycomb lattice material Na 2 IrO 3 journal August 2010
Effects of Stacking Fault Defects on the X-ray Diffraction Patterns of T2, O2, and O6 Structure Li 2/3 [Co x Ni 1/3 - x Mn 2/3 ]O 2 journal June 2001
High-resolution X-ray diffraction, DIFFaX, NMR and first principles study of disorder in the Li2MnO3–Li[Ni1/2Mn1/2]O2 solid solution journal September 2005
Cathode characteristics of layered rocksalt oxide, Li2PtO3 journal September 1999
Visualization of O-O peroxo-like dimers in high-capacity layered oxides for Li-ion batteries journal December 2015
Photo- and radioluminescence of lithium hafnate Li2HfO3 journal May 2012
Implementation of the projector augmented-wave method in the ABINIT code: Application to the study of iron under pressure journal April 2008
Charge transfer instability in a mixed Ir/Rh honeycomb lattice in Li2Ir1−xRhxO3 solid solution journal November 2016
Neutron profile refinement of the structures of Li2SnO3 and Li2ZrO3 journal November 1982
Structure of Two Disordered Molybdates, Li 2 Mo IV O 3 and Li 4 Mo 3 IV O 8 , from Total Neutron Scattering journal August 1997
Interplay between spin-orbit coupling and strong correlation effects: Comparison of the three osmate double perovskites Ba 2 A OsO 6 ( A = Na , Ca, Y) journal April 2016
Na 2 IrO 3 as a Molecular Orbital Crystal journal November 2012
Strongly Geometrically Frustrated Magnets journal August 1994
Structure and properties of ordered Li2IrO3 and Li2PtO3 journal August 2008
First-Principles Study of the Honeycomb-Lattice Iridates Na 2 IrO 3 in the Presence of Strong Spin-Orbit Interaction and Electron Correlations journal September 2014
Strong magnetic frustration and anti-site disorder causing spin-glass behavior in honeycomb Li2RhO3 journal October 2015
Strongly Geometrically Frustrated Magnets journal January 1994
Structural and Anisotropic Thermal Expansion Correlation of Li 2 ZrO 3 at Different Temperatures journal August 2000
Neutron scattering in the proximate quantum spin liquid α-RuCl3. text January 2017
Na2IrO3 as a molecular orbital crystal text January 2012
Origin of the insulating state in honeycomb iridates and rhodates text January 2013
The Insulating Nature of Na2IrO3: Mott-type or Slater-type? text January 2015
Anyons in an exactly solved model and beyond text January 2005

Figures / Tables (9)