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Title: Spin-glass behavior and vacancy order in van der Waals layered β - MoCl 4

Abstract

Two-dimensional $${\beta}\text{-}{\mathrm{MoCl}}_{4}$$ is an attractive material from the perspectives of magnetism in $4d$ transition metal compounds, geometrically frustrated lattices, and magnetic van der Waals layered materials, but the magnetism in this compound has not been particularly well studied to date. In this paper the magnetic properties and crystal structure of $${\mathrm{MoCl}}_{4}$$ are revisited, and results of ac and dc magnetic measurements and single crystal x-ray diffraction are reported. Crystals grow as well-formed and easily cleaved hexagonal plates that are unstable in air. The revised structural model comprises $${\mathrm{CdCl}}_{2}$$-type layers with 50% Mo vacancies distributed over the sites of the triangular cation net. Interestingly, a structural ambiguity regarding the vacancy distribution is identified in the analysis of the diffraction data. The orbital moment is not expected to be quenched in this $$4{d}^{2}$$ compound. Accordingly, magnetization measurements indicate an effective moment that is about 20% lower than the spin-only value. The magnetic data reveal an anomaly near 5 K, below which a divergence of field-cooled and zero-field-cooled dc magnetization, a slow relaxation of thermoremanent magnetization, and enhanced frequency dependence of ac magnetization are observed. Finally and thus, $${\beta}\text{-}{\mathrm{MoCl}}_{4}$$ represents an uncommon example of a cleavable spin-glass system.

Authors:
 [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Materials Science and Technology Division
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) (SC-22)
OSTI Identifier:
1462846
Alternate Identifier(s):
OSTI ID: 1462140
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review Materials
Additional Journal Information:
Journal Volume: 2; Journal Issue: 7; Journal ID: ISSN 2475-9953
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; crystal structure; magnetism; spin glasses; AC susceptibility measurements; crystallography; DC susceptibility measurements

Citation Formats

McGuire, Michael A., and Sales, Brian C. Spin-glass behavior and vacancy order in van der Waals layered β-MoCl4. United States: N. p., 2018. Web. doi:10.1103/PhysRevMaterials.2.074007.
McGuire, Michael A., & Sales, Brian C. Spin-glass behavior and vacancy order in van der Waals layered β-MoCl4. United States. doi:10.1103/PhysRevMaterials.2.074007.
McGuire, Michael A., and Sales, Brian C. Mon . "Spin-glass behavior and vacancy order in van der Waals layered β-MoCl4". United States. doi:10.1103/PhysRevMaterials.2.074007. https://www.osti.gov/servlets/purl/1462846.
@article{osti_1462846,
title = {Spin-glass behavior and vacancy order in van der Waals layered β-MoCl4},
author = {McGuire, Michael A. and Sales, Brian C.},
abstractNote = {Two-dimensional ${\beta}\text{-}{\mathrm{MoCl}}_{4}$ is an attractive material from the perspectives of magnetism in $4d$ transition metal compounds, geometrically frustrated lattices, and magnetic van der Waals layered materials, but the magnetism in this compound has not been particularly well studied to date. In this paper the magnetic properties and crystal structure of ${\mathrm{MoCl}}_{4}$ are revisited, and results of ac and dc magnetic measurements and single crystal x-ray diffraction are reported. Crystals grow as well-formed and easily cleaved hexagonal plates that are unstable in air. The revised structural model comprises ${\mathrm{CdCl}}_{2}$-type layers with 50% Mo vacancies distributed over the sites of the triangular cation net. Interestingly, a structural ambiguity regarding the vacancy distribution is identified in the analysis of the diffraction data. The orbital moment is not expected to be quenched in this $4{d}^{2}$ compound. Accordingly, magnetization measurements indicate an effective moment that is about 20% lower than the spin-only value. The magnetic data reveal an anomaly near 5 K, below which a divergence of field-cooled and zero-field-cooled dc magnetization, a slow relaxation of thermoremanent magnetization, and enhanced frequency dependence of ac magnetization are observed. Finally and thus, ${\beta}\text{-}{\mathrm{MoCl}}_{4}$ represents an uncommon example of a cleavable spin-glass system.},
doi = {10.1103/PhysRevMaterials.2.074007},
journal = {Physical Review Materials},
number = 7,
volume = 2,
place = {United States},
year = {2018},
month = {7}
}

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    Works referencing / citing this record:

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    journal, August 1981

    • Müller, Ulrich
    • Angewandte Chemie International Edition in English, Vol. 20, Issue 8
    • DOI: 10.1002/anie.198106921

    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

    Phase diagram, magnetic properties and specific heat of Mn1−xFexPS3
    journal, July 2008

    • Masubuchi, Toshihiro; Hoya, Hisanobu; Watanabe, Tadataka
    • Journal of Alloys and Compounds, Vol. 460, Issue 1-2
    • DOI: 10.1016/j.jallcom.2007.06.063

    Magnetic structure and glassiness in
    journal, May 2013

    • Goossens, D. J.; Brazier-Hollins, S.; James, D. R.
    • Journal of Magnetism and Magnetic Materials, Vol. 334
    • DOI: 10.1016/j.jmmm.2013.01.023

    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

    Synthesis of Molybdenum Tetrachloride
    journal, February 1964


    .alpha.-Molybdenum tetrachloride. A structural isomer containing molybdenum-molybdenum interactions
    journal, October 1968

    • Kepert, D. L.; Mandyczewsky, R.
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    • DOI: 10.1021/ic50068a029

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    journal, July 2013

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    • Nature, Vol. 499, Issue 7459, p. 419-425
    • DOI: 10.1038/nature12385

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    journal, April 2017


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    journal, June 2017

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

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    journal, April 2018


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    journal, May 2016

    • Korotin, Dmitry M.; Anisimov, Vladimir I.; Streltsov, Sergey V.
    • Scientific Reports, Vol. 6, Issue 1
    • DOI: 10.1038/srep25831

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    journal, May 2003

    • Takano, Yoshiki; Arai, Atsuko; Takahashi, Yumiko
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    • DOI: 10.1063/1.1539078

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    • Hansen, Wilford N.; Griffel, Maurice
    • The Journal of Chemical Physics, Vol. 28, Issue 5
    • DOI: 10.1063/1.1744294

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    journal, May 2018


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