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Title: Theoretical study of the crystal and electronic properties of α - RuI 3

Abstract

The material α-RuCl3, with a two-dimensional Ru honeycomb sublattice, has attracted considerable attention because it may be a realization of the Kitaev quantum spin liquid. Recently, a new honeycomb material, α-RuCl3, was prepared under moderately high pressure, and it is stable under ambient conditions. However, different from α-RuCl3, α-RuI3 was reported to be a paramagnetic metal without long-range magnetic order down to 0.35 K. Here, the structural and electronic properties of the quasi-two-dimensional α-RuI3 are theoretically studied. First, based on first-principles density functional theory calculations, the ABC stacking honeycomb-layer R$$\bar{3}$$ (No. 148) structure is found to be the most likely stacking order for α-RuI3 along the c axis. Furthermore, both R$$\bar{3}$$ and P$$\bar{3}$$1c are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum without Hubbard U. Moreover, the different physical behavior of α-RuI3 compared to α-RuCl3 can be understood naturally. The strong hybridization between Ru 4d and I 5p orbitals decreases the “effective” atomic Hubbard repulsion, leading the electrons of RuI3 to be less localized than in RuCl3. As a consequence, the effective electronic correlation is reduced from Cl to I, leading to the metallic nature of α-RuI3. Based on the DFT+U (Ueff=2 eV) plus spin-orbital coupling, we obtained a spin-orbit Mott insulating behavior for α-RuCl3 and, with the same procedure, a metallic behavior for α-RuI3, in good agreement with experimental results. Furthermore, when introducing large (unrealistic) Ueff=6 eV, the spin-orbit Mott gap opens in α-RuI3 as well, supporting the physical picture we are proposing. Our results provide guidance to experimentalists and theorists working on two-dimensional transition metal tri-iodide layered materials.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2];  [2]
  1. Univ. of Tennessee, Knoxville, TN (United States)
  2. Univ. of Tennessee, Knoxville, TN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division
OSTI Identifier:
1870232
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review. B
Additional Journal Information:
Journal Volume: 105; Journal Issue: 8; Journal ID: ISSN 2469-9950
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; electronic structure; 2-dimensional systems; honeycomb lattice; strongly correlated systems; density functional calculations; first-principles calculations

Citation Formats

Zhang, Yang, Lin, Ling-Fang, Moreo, Adriana, and Dagotto, Elbio. Theoretical study of the crystal and electronic properties of α-RuI3. United States: N. p., 2022. Web. doi:10.1103/physrevb.105.085107.
Zhang, Yang, Lin, Ling-Fang, Moreo, Adriana, & Dagotto, Elbio. Theoretical study of the crystal and electronic properties of α-RuI3. United States. https://doi.org/10.1103/physrevb.105.085107
Zhang, Yang, Lin, Ling-Fang, Moreo, Adriana, and Dagotto, Elbio. Fri . "Theoretical study of the crystal and electronic properties of α-RuI3". United States. https://doi.org/10.1103/physrevb.105.085107. https://www.osti.gov/servlets/purl/1870232.
@article{osti_1870232,
title = {Theoretical study of the crystal and electronic properties of α-RuI3},
author = {Zhang, Yang and Lin, Ling-Fang and Moreo, Adriana and Dagotto, Elbio},
abstractNote = {The material α-RuCl3, with a two-dimensional Ru honeycomb sublattice, has attracted considerable attention because it may be a realization of the Kitaev quantum spin liquid. Recently, a new honeycomb material, α-RuCl3, was prepared under moderately high pressure, and it is stable under ambient conditions. However, different from α-RuCl3, α-RuI3 was reported to be a paramagnetic metal without long-range magnetic order down to 0.35 K. Here, the structural and electronic properties of the quasi-two-dimensional α-RuI3 are theoretically studied. First, based on first-principles density functional theory calculations, the ABC stacking honeycomb-layer R$\bar{3}$ (No. 148) structure is found to be the most likely stacking order for α-RuI3 along the c axis. Furthermore, both R$\bar{3}$ and P$\bar{3}$1c are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum without Hubbard U. Moreover, the different physical behavior of α-RuI3 compared to α-RuCl3 can be understood naturally. The strong hybridization between Ru 4d and I 5p orbitals decreases the “effective” atomic Hubbard repulsion, leading the electrons of RuI3 to be less localized than in RuCl3. As a consequence, the effective electronic correlation is reduced from Cl to I, leading to the metallic nature of α-RuI3. Based on the DFT+U (Ueff=2 eV) plus spin-orbital coupling, we obtained a spin-orbit Mott insulating behavior for α-RuCl3 and, with the same procedure, a metallic behavior for α-RuI3, in good agreement with experimental results. Furthermore, when introducing large (unrealistic) Ueff=6 eV, the spin-orbit Mott gap opens in α-RuI3 as well, supporting the physical picture we are proposing. Our results provide guidance to experimentalists and theorists working on two-dimensional transition metal tri-iodide layered materials.},
doi = {10.1103/physrevb.105.085107},
journal = {Physical Review. B},
number = 8,
volume = 105,
place = {United States},
year = {Fri Feb 04 00:00:00 EST 2022},
month = {Fri Feb 04 00:00:00 EST 2022}
}

Works referenced in this record:

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

Exploring the electronic and magnetic properties of new metal halides from bulk to two-dimensional monolayer: RuX3 (X = Br, I)
journal, April 2019

  • Ersan, Fatih; Vatansever, Erol; Sarikurt, Sevil
  • Journal of Magnetism and Magnetic Materials, Vol. 476
  • DOI: 10.1016/j.jmmm.2018.12.032

Projector augmented-wave method
journal, December 1994


Effective Coulomb interaction in transition metals from constrained random-phase approximation
journal, March 2011


Dynamic Spin Correlations in the Honeycomb Lattice Na 2 IrO 3 Measured by Resonant Inelastic x-Ray Scattering
journal, May 2020


Excitations in the field-induced quantum spin liquid state of α-RuCl3
journal, February 2018

  • Banerjee, Arnab; Lampen-Kelley, Paula; Knolle, Johannes
  • npj Quantum Materials, Vol. 3, Issue 1
  • DOI: 10.1038/s41535-018-0079-2

Correlated Quantum Phenomena in the Strong Spin-Orbit Regime
journal, March 2014


Tendencies in ABO3 Perovskite and SrF2, BaF2 and CaF2 Bulk and Surface F-Center Ab Initio Computations at High Symmetry Cubic Structure
journal, October 2021

  • Eglitis, Roberts I.; Purans, Juris; Popov, Anatoli I.
  • Symmetry, Vol. 13, Issue 10
  • DOI: 10.3390/sym13101920

Magnetoelectricity in multiferroics: a theoretical perspective
journal, February 2019

  • Dong, Shuai; Xiang, Hongjun; Dagotto, Elbio
  • National Science Review, Vol. 6, Issue 4
  • DOI: 10.1093/nsr/nwz023

Recent ARPES experiments on quasi-1D bulk materials and artificial structures
journal, December 2008


Origin of Insulating Ferromagnetism in Iron Oxychalcogenide Ce 2 O 2 FeSe 2
journal, August 2021


Evidence for a Field-Induced Quantum Spin Liquid in α - RuCl 3
journal, July 2017


Iron-Based Layered Superconductor La[O 1- x F x ]FeAs ( x = 0.05−0.12) with T c = 26 K
journal, March 2008

  • Kamihara, Yoichi; Watanabe, Takumi; Hirano, Masahiro
  • Journal of the American Chemical Society, Vol. 130, Issue 11
  • DOI: 10.1021/ja800073m

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

VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data
journal, October 2011


Magnetic states of the quasi-one-dimensional iron chalcogenide Ba 2 FeS 3
journal, September 2021


Properties of La 0.7 Ca 0.3 MnO 3 under extreme tensile strain
journal, July 2020


Orbital-selective Peierls phase in the metallic dimerized chain MoOCl 2
journal, August 2021


Peierls transition, ferroelectricity, and spin-singlet formation in monolayer VOI 2
journal, March 2021


Successive magnetic phase transitions in α RuCl 3 : XY-like frustrated magnet on the honeycomb lattice
journal, March 2015


Gapless Spin Excitations in the Field-Induced Quantum Spin Liquid Phase of α RuCl 3
journal, December 2017


Fingerprints of an orbital-selective Mott phase in the block magnetic state of BaFe2Se3 ladders
journal, June 2019


The J eff = 1/2 Antiferromagnet Sr 2 IrO 4 : A Golden Avenue toward New Physics and Functions
journal, October 2019


α RuCl 3 : A spin-orbit assisted Mott insulator on a honeycomb lattice
journal, July 2014


Orbital-dependent singlet dimers and orbital-selective Peierls transitions in transition-metal compounds
journal, April 2014


Electronic crystals: an experimental overview
journal, August 2012


Origin of the magnetic and orbital ordering in α Sr 2 Cr O 4
journal, January 2021


Ab initiomolecular dynamics for liquid metals
journal, January 1993


Superconductivity in iron compounds
journal, December 2011


Kitaev-Heisenberg Model on a Honeycomb Lattice: Possible Exotic Phases in Iridium Oxides A 2 IrO 3
journal, July 2010


Crystal structure and magnetism in α RuCl 3 : An ab initio study
journal, April 2016


Optical and transport properties of the magnetic semiconductor α-RuCl3
journal, March 1971


Hubbard U and Hund exchange J in transition metal oxides: Screening versus localization trends from constrained random phase approximation
journal, October 2012


Deriving models for the Kitaev spin-liquid candidate material α RuCl 3 from first principles
journal, August 2019


Orbital ordering in the layered perovskite material CsVF 4
journal, February 2021


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010

  • Grimme, Stefan; Antony, Jens; Ehrlich, Stephan
  • The Journal of Chemical Physics, Vol. 132, Issue 15
  • DOI: 10.1063/1.3382344

Oxygen magnetic polarization, nodes in spin density, and zigzag spin order in oxides
journal, May 2021


Colloquium : The unexpected properties of alkali metal iron selenide superconductors
journal, May 2013


Phonon-phonon interactions in transition metals
journal, September 2011


Low-temperature crystal and magnetic structure of α RuCl 3
journal, April 2016


Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

  • Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars
  • Journal of Computational Chemistry, Vol. 32, Issue 7
  • DOI: 10.1002/jcc.21759

Colossal magnetoresistant materials: the key role of phase separation
journal, April 2001


Proximate Kitaev quantum spin liquid behaviour in a honeycomb magnet
journal, April 2016

  • Banerjee, A.; Bridges, C. A.; Yan, J. -Q.
  • Nature Materials, Vol. 15, Issue 7
  • DOI: 10.1038/nmat4604

Honeycomb‐Structure RuI 3 , A New Quantum Material Related to α‐RuCl 3
journal, January 2022


Anyons in an exactly solved model and beyond
journal, January 2006


Monoclinic crystal structure of α RuCl 3 and the zigzag antiferromagnetic ground state
journal, December 2015


Unusual Thermal Hall Effect in a Kitaev Spin Liquid Candidate α RuCl 3
journal, May 2018


Complexity in Strongly Correlated Electronic Systems
journal, July 2005


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


Possible highT c superconductivity in the Ba?La?Cu?O system
journal, June 1986

  • Bednorz, J. G.; M�ller, K. A.
  • Zeitschrift f�r Physik B Condensed Matter, Vol. 64, Issue 2
  • DOI: 10.1007/BF01303701

Neutron scattering in the proximate quantum spin liquid α-RuCl 3
journal, June 2017


Novel Magnetic Block States in Low-Dimensional Iron-Based Superconductors
journal, July 2019


Direct experimental evidence of physical origin of electronic phase separation in manganites
journal, March 2020

  • Miao, Tian; Deng, Lina; Yang, Wenting
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 13
  • DOI: 10.1073/pnas.1920502117

Electronic properties of the narrow-band material α- RuCl 3
journal, May 1996


Generic Spin Model for the Honeycomb Iridates beyond the Kitaev Limit
journal, February 2014


Majorana quantization and half-integer thermal quantum Hall effect in a Kitaev spin liquid
journal, July 2018


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


First principles phonon calculations in materials science
journal, November 2015


Relevance of the Heisenberg-Kitaev Model for the Honeycomb Lattice Iridates A 2 IrO 3
journal, March 2012


Spin Waves and Revised Crystal Structure of Honeycomb Iridate Na 2 IrO 3
journal, March 2012


Correlated electrons in high-temperature superconductors
journal, July 1994


Majorana fermions in the Kitaev quantum spin system α-RuCl3
journal, September 2017

  • Do, Seung-Hwan; Park, Sang-Youn; Yoshitake, Junki
  • Nature Physics, Vol. 13, Issue 11
  • DOI: 10.1038/nphys4264

Kitaev magnetism in honeycomb RuCl 3 with intermediate spin-orbit coupling
journal, June 2015


Superconductivity in an infinite-layer nickelate
journal, August 2019


Restoring the Density-Gradient Expansion for Exchange in Solids and Surfaces
journal, April 2008


Electron Localization in Solid-State Structures of the Elements: the Diamond Structure
journal, February 1992

  • Savin, Andreas; Jepsen, Ove; Flad, Jürgen
  • Angewandte Chemie International Edition in English, Vol. 31, Issue 2
  • DOI: 10.1002/anie.199201871

Relation between Kitaev magnetism and structure in α RuCl 3
journal, May 2017


Orbital-Selective Mott Transition out of Band Degeneracy Lifting
journal, March 2009


Nonmonotonic crossover in electronic phase separated manganite superlattices driven by the superlattice period
journal, December 2020


Ferroelectric ferrimagnetic LiFe 2 F 6 : Charge-ordering-mediated magnetoelectricity
journal, December 2017


Strongly Electron-Correlated Semimetal RuI 3 with a Layered Honeycomb Structure
journal, December 2021

  • Nawa, Kazuhiro; Imai, Yoshinori; Yamaji, Youhei
  • Journal of the Physical Society of Japan, Vol. 90, Issue 12
  • DOI: 10.7566/JPSJ.90.123703

Frustrated Dipole Order Induces Noncollinear Proper Ferrielectricity in Two Dimensions
journal, August 2019


Multiferroicity due to charge ordering
journal, October 2008


Magnetism and its microscopic origin in iron-based high-temperature superconductors
journal, October 2012

  • Dai, Pengcheng; Hu, Jiangping; Dagotto, Elbio
  • Nature Physics, Vol. 8, Issue 10
  • DOI: 10.1038/nphys2438

Spin-orbit excitations and electronic structure of the putative Kitaev magnet α RuCl 3
journal, February 2016


Quasi-one-dimensional ferroelectricity and piezoelectricity in WO X 4 halogens
journal, November 2019


Pressure-induced dimerization and valence bond crystal formation in the Kitaev-Heisenberg magnet α RuCl 3
journal, June 2018


Quantum anomalous Hall effect in ferromagnetic transition metal halides
journal, January 2017


Iron telluride ladder compounds: Predicting the structural and magnetic properties of BaFe 2 Te 3
journal, April 2020


Mott Insulators in the Strong Spin-Orbit Coupling Limit: From Heisenberg to a Quantum Compass and Kitaev Models
journal, January 2009


J eff Description of the Honeycomb Mott Insulator α RuCl 3
journal, September 2016


Na 2 IrO 3 as a Molecular Orbital Crystal
journal, November 2012


A common thread: The pairing interaction for unconventional superconductors
journal, October 2012


Orbital Physics in Transition-Metal Oxides
journal, April 2000


Raman spectroscopy evidence for dimerization and Mott collapse in α RuCl 3 under pressures
journal, February 2019


Block–spiral magnetism: An exotic type of frustrated order
journal, June 2020

  • Herbrych, J.; Heverhagen, J.; Alvarez, G.
  • Proceedings of the National Academy of Sciences, Vol. 117, Issue 28
  • DOI: 10.1073/pnas.2001141117