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Title: High-temperature magnetostructural transition in van der Waals-layered α - MoCl 3

Abstract

Here, the crystallographic and magnetic properties of the cleavable 4d3 transition metal compound α–MoCl3 are reported, with a focus on the behavior above room temperature. Crystals were grown by chemical vapor transport and characterized using temperature dependent x-ray diffraction, Raman spectroscopy, and magnetization measurements. A structural phase transition occurs near 585 K, at which the Mo-Mo dimers present at room temperature are broken. A nearly regular honeycomb net of Mo is observed above the transition, and an optical phonon associated with the dimerization instability is identified in the Raman data and in first-principles calculations. The crystals are diamagnetic at room temperature in the dimerized state, and the magnetic susceptibility increases sharply at the structural transition. Moderately strong paramagnetism in the high-temperature structure indicates the presence of local moments on Mo. This is consistent with results of spin-polarized density functional theory calculations using the low- and high-temperature structures. Above the magnetostructural phase transition the magnetic susceptibility continues to increase gradually up to the maximum measurement temperature of 780 K, with a temperature dependence that suggests two-dimensional antiferromagnetic correlations.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. 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)
OSTI Identifier:
1407774
Alternate Identifier(s):
OSTI ID: 1407843
Grant/Contract Number:  
AC05-00OR22725; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 1; Journal Issue: 6; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

McGuire, Michael A., Yan, Jiaqiang, Lampen-Kelley, Paula, May, Andrew F., Cooper, Valentino R., Lindsay, Lucas R., Puretzky, Alexander A., Liang, Liangbo, KC, Santosh, Cakmak, Ercan, Calder, Stuart, and Sales, Brian C. High-temperature magnetostructural transition in van der Waals-layered α-MoCl3. United States: N. p., 2017. Web. doi:10.1103/PhysRevMaterials.1.064001.
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McGuire, Michael A., Yan, Jiaqiang, Lampen-Kelley, Paula, May, Andrew F., Cooper, Valentino R., Lindsay, Lucas R., Puretzky, Alexander A., Liang, Liangbo, KC, Santosh, Cakmak, Ercan, Calder, Stuart, & Sales, Brian C. High-temperature magnetostructural transition in van der Waals-layered α-MoCl3. United States. https://doi.org/10.1103/PhysRevMaterials.1.064001
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McGuire, Michael A., Yan, Jiaqiang, Lampen-Kelley, Paula, May, Andrew F., Cooper, Valentino R., Lindsay, Lucas R., Puretzky, Alexander A., Liang, Liangbo, KC, Santosh, Cakmak, Ercan, Calder, Stuart, and Sales, Brian C. Tue . "High-temperature magnetostructural transition in van der Waals-layered α-MoCl3". United States. https://doi.org/10.1103/PhysRevMaterials.1.064001. https://www.osti.gov/servlets/purl/1407774.
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@article{osti_1407774,
title = {High-temperature magnetostructural transition in van der Waals-layered α-MoCl3},
author = {McGuire, Michael A. and Yan, Jiaqiang and Lampen-Kelley, Paula and May, Andrew F. and Cooper, Valentino R. and Lindsay, Lucas R. and Puretzky, Alexander A. and Liang, Liangbo and KC, Santosh and Cakmak, Ercan and Calder, Stuart and Sales, Brian C.},
abstractNote = {Here, the crystallographic and magnetic properties of the cleavable 4d3 transition metal compound α–MoCl3 are reported, with a focus on the behavior above room temperature. Crystals were grown by chemical vapor transport and characterized using temperature dependent x-ray diffraction, Raman spectroscopy, and magnetization measurements. A structural phase transition occurs near 585 K, at which the Mo-Mo dimers present at room temperature are broken. A nearly regular honeycomb net of Mo is observed above the transition, and an optical phonon associated with the dimerization instability is identified in the Raman data and in first-principles calculations. The crystals are diamagnetic at room temperature in the dimerized state, and the magnetic susceptibility increases sharply at the structural transition. Moderately strong paramagnetism in the high-temperature structure indicates the presence of local moments on Mo. This is consistent with results of spin-polarized density functional theory calculations using the low- and high-temperature structures. Above the magnetostructural phase transition the magnetic susceptibility continues to increase gradually up to the maximum measurement temperature of 780 K, with a temperature dependence that suggests two-dimensional antiferromagnetic correlations.},
doi = {10.1103/PhysRevMaterials.1.064001},
journal = {Physical Review Materials},
number = 6,
volume = 1,
place = {United States},
year = {Tue Nov 07 00:00:00 EST 2017},
month = {Tue Nov 07 00:00:00 EST 2017}
}
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https://doi.org/10.1103/PhysRevMaterials.1.064001
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Works referenced in this record:

Calculation of the lattice constant of solids with semilocal functionals
journal, February 2009

Dimensional diversity in transition metal trihalides
journal, April 1993

  • Lin, Jianhua; Miller, Gordon J.
  • Inorganic Chemistry, Vol. 32, Issue 8
  • DOI: 10.1021/ic00060a025

Exfoliating biocompatible ferromagnetic Cr-trihalide monolayers
journal, January 2016

  • Liu, Junyi; Sun, Qiang; Kawazoe, Yoshiyuki
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 13
  • DOI: 10.1039/C5CP04835D

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

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

X‐Ray Diffraction and Nuclear Quadrupole Resonance Studies of Chromium Trichloride
journal, April 1964

  • Morosin, Bruno; Narath, Albert
  • The Journal of Chemical Physics, Vol. 40, Issue 7
  • DOI: 10.1063/1.1725428

High antiferromagnetic transition temperature of the honeycomb compound SrRu 2 O 6
journal, September 2015

Spin-Wave Renormalization Applied to Ferromagnetic Cr Br 3
journal, April 1964

Structural and scanning microscopy studies of layered compounds MCl3 (M = Mo, Ru, Cr) and MOCl2 (M = V, Nb, Mo, Ru, Os)
journal, January 1997

Phonons and related crystal properties from density-functional perturbation theory
journal, July 2001

  • Baroni, Stefano; de Gironcoli, Stefano; Dal Corso, Andrea
  • Reviews of Modern Physics, Vol. 73, Issue 2
  • DOI: 10.1103/RevModPhys.73.515

Die Kristallstrukturen von ScCl3, TiCl3 und VCl3
journal, May 1947

  • Klemm, Wilhelm; Krose, Ehrhard
  • Zeitschrift f�r anorganische Chemie, Vol. 253, Issue 3-4
  • DOI: 10.1002/zaac.19472530313

New-Type Phase Transition of Li 2 RuO 3 with Honeycomb Structure
journal, March 2007

  • Miura, Yoko; Yasui, Yukio; Sato, Masatoshi
  • Journal of the Physical Society of Japan, Vol. 76, Issue 3
  • DOI: 10.1143/JPSJ.76.033705

Multiferroicity in NiBr 2 with long-wavelength cycloidal spin structure on a triangular lattice
journal, August 2011

Neue Untersuchungen �ber die Chloride des Molybd�ns
journal, September 1967

  • Sch�fer, H.; Schnering, H. -G. V.; Tillack, J.
  • Zeitschrift f�r anorganische und allgemeine Chemie, Vol. 353, Issue 5-6
  • DOI: 10.1002/zaac.19673530510

Strukturuntersuchungen an Rhodiumhalogeniden
journal, January 1968

QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials
journal, September 2009

  • Giannozzi, Paolo; Baroni, Stefano; Bonini, Nicola
  • Journal of Physics: Condensed Matter, Vol. 21, Issue 39, Article No. 395502
  • DOI: 10.1088/0953-8984/21/39/395502

β-Technetium Trichloride: Formation, Structure, and First-Principles Calculations
journal, April 2012

  • Poineau, Frederic; Johnstone, Erik V.; Weck, Philippe F.
  • Inorganic Chemistry, Vol. 51, Issue 9
  • DOI: 10.1021/ic300612k

Evidencing the existence of exciting half-metallicity in two-dimensional TiCl3 and VCl3 sheets
journal, January 2016

  • Zhou, Yungang; Lu, Haifeng; Zu, Xiaotao
  • Scientific Reports, Vol. 6, Issue 1
  • DOI: 10.1038/srep19407

Magnetic Susceptibilities and Ionic Moments in the Palladium and Platinum Groups
journal, February 1931

Coupling of Crystal Structure and Magnetism in the Layered, Ferromagnetic Insulator CrI 3
journal, January 2015

  • McGuire, Michael A.; Dixit, Hemant; Cooper, Valentino R.
  • Chemistry of Materials, Vol. 27, Issue 2
  • DOI: 10.1021/cm504242t

Valence bond liquid phase in the honeycomb lattice material Li 2 Ru O 3
journal, February 2014

Crystal and Magnetic Structures in Layered, Transition Metal Dihalides and Trihalides
journal, April 2017

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

Antiferromagnetism at T > 500 K in the layered hexagonal ruthenate SrR u 2 O 6
journal, September 2015

Van der Waals Density Functional for General Geometries
journal, June 2004

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

Low-temperature heat capacities of molybdenum tri- and tetrachlorides
journal, June 1975

Van der Waals density functional: An appropriate exchange functional
journal, April 2010

Layer-dependent ferromagnetism in a van der Waals crystal down to the monolayer limit
journal, June 2017

  • Huang, Bevin; Clark, Genevieve; Navarro-Moratalla, Efrén
  • Nature, Vol. 546, Issue 7657
  • DOI: 10.1038/nature22391

Magnetic Transition in TiCl 3
journal, October 1960

  • Ogawa, Shinji
  • Journal of the Physical Society of Japan, Vol. 15, Issue 10
  • DOI: 10.1143/JPSJ.15.1901

Electrical properties of α-TiCl3 crystals
journal, October 1970

  • Cavallone, F.; Pollini, I.; Spinolo, G.
  • Lettere al Nuovo Cimento, Vol. 4, Issue 17
  • DOI: 10.1007/BF02755337

Spin-Wave Analysis of the Sublattice Magnetization Behavior of Antiferromagnetic and Ferromagnetic Cr Cl 3
journal, January 1965

Direct Cation-Cation Interactions in Primarily Ionic Solids
journal, May 1960

  • Goodenough, John B.
  • Journal of Applied Physics, Vol. 31, Issue 5
  • DOI: 10.1063/1.1984748

On the Magnetic Properties of a CrBr 3 Single Crystal
journal, September 1960

  • Tsubokawa, Ichiro
  • Journal of the Physical Society of Japan, Vol. 15, Issue 9
  • DOI: 10.1143/JPSJ.15.1664

Unusual Dirac half-metallicity with intrinsic ferromagnetism in vanadium trihalide monolayers
journal, January 2016

  • He, Junjie; Ma, Shuangying; Lyu, Pengbo
  • Journal of Materials Chemistry C, Vol. 4, Issue 13
  • DOI: 10.1039/C6TC00409A

Van der Waals engineering of ferromagnetic semiconductor heterostructures for spin and valleytronics
journal, May 2017

First-order magnetostructural transition in single crystals of the honeycomb lattice ruthenate Li 2 RuO 3
journal, February 2017

Neutron diffraction investigation of antiferromagnetism in CrCl3
journal, April 1961

  • Cable, J. W.; Wilkinson, M. K.; Wollan, E. O.
  • Journal of Physics and Chemistry of Solids, Vol. 19, Issue 1-2
  • DOI: 10.1016/0022-3697(61)90053-1

Robust intrinsic ferromagnetism and half semiconductivity in stable two-dimensional single-layer chromium trihalides
journal, January 2015

  • Zhang, Wei-Bing; Qu, Qian; Zhu, Peng
  • Journal of Materials Chemistry C, Vol. 3, Issue 48
  • DOI: 10.1039/C5TC02840J

Recent Advances in Technetium Halide Chemistry
journal, December 2013

  • Poineau, Frederic; Johnstone, Erik V.; Czerwinski, Kenneth R.
  • Accounts of Chemical Research, Vol. 47, Issue 2
  • DOI: 10.1021/ar400225b

High Temperature Magnetic Ordering in the 4 d Perovskite SrTcO 3
journal, February 2011

Manifestation of long-range ordered state in layered VX 2 (X = Cl, Br, I) systems
journal, October 2013

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

Layer-dependent Ferromagnetism in a van der Waals Crystal down to the Monolayer Limit
text, January 2017

New Type Phase Transition of Li2RuO3 with Honeycomb Structure
text, January 2006

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    Works referencing / citing this record:

    Neutron Instruments for Research in Coordination Chemistry: Neutron Instruments for Research in Coordination Chemistry
    journal, January 2019

    • Xue, Zi-Ling; Ramirez-Cuesta, Anibal J.; Brown, Craig M.
    • European Journal of Inorganic Chemistry, Vol. 2019, Issue 8
    • DOI: 10.1002/ejic.201801076

    Chemical Vapor Transport Reactions for Synthesizing Layered Materials and Their 2D Counterparts
    journal, September 2019

    A suite-level review of the neutron powder diffraction instruments at Oak Ridge National Laboratory
    journal, September 2018

    • Calder, S.; An, K.; Boehler, R.
    • Review of Scientific Instruments, Vol. 89, Issue 9
    • DOI: 10.1063/1.5033906

    Phonon anomalies near the magnetostructural transition in Li 2 RuO 3 : Raman spectroscopy and density functional theory studies
    journal, October 2019

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