Iridate Li8IrO6: An Antiferromagnetic Insulator

Callista M. Skaggs; Peter E. Siegfried; Chang Jong Kang; Craig M. Brown; Fu Chen; Lu Ma; Steven N. Ehrlich; Yan Xin; Mark Croft; Wenqian Xu; Saul H. Lapidus; Nirmal J. Ghimire; Xiaoyan Tan

doi:10.1021/acs.inorgchem.1c02535

Iridate Li₈IrO₆: An Antiferromagnetic Insulator

Callista M. Skaggs, Peter E. Siegfried, Chang Jong Kang, Craig M. Brown, Fu Chen, Lu Ma, Steven N. Ehrlich, Yan Xin, Mark Croft, Wenqian Xu, Saul H. Lapidus, Nirmal J. Ghimire, Xiaoyan Tan

School of Arts and Sciences, Physics & Astronomy

Research output: Contribution to journal › Article › peer-review

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Abstract

A polycrystalline iridate Li8IrO6 material was prepared via heating Li2O and IrO2 starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li8IrO6 adopts the nonpolar space group R3¯ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state 7Li NMR. This results in a crystal structure consisting of LiO4 tetrahedral layers alternating with mixed IrO6 and LiO6 octahedral layers along the crystallographic c-axis. The +4 oxidation state of Ir4+ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li8IrO6 indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a Néel temperature (TN) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment μeff (Ir) = 1.73 μB and insulating character indicate that Li8IrO6 is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.

Original language	English (US)
Pages (from-to)	17201-17211
Number of pages	11
Journal	Inorganic Chemistry
Volume	60
Issue number	22
DOIs	https://doi.org/10.1021/acs.inorgchem.1c02535
State	Published - Nov 15 2021

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/acs.inorgchem.1c02535

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@article{85e0b76deea64001bea0b27ed90c3691,

title = "Iridate Li8IrO6: An Antiferromagnetic Insulator",

abstract = "A polycrystalline iridate Li8IrO6 material was prepared via heating Li2O and IrO2 starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li8IrO6 adopts the nonpolar space group R3¯ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state 7Li NMR. This results in a crystal structure consisting of LiO4 tetrahedral layers alternating with mixed IrO6 and LiO6 octahedral layers along the crystallographic c-axis. The +4 oxidation state of Ir4+ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li8IrO6 indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a N{\'e}el temperature (TN) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment μeff (Ir) = 1.73 μB and insulating character indicate that Li8IrO6 is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.",

author = "Skaggs, {Callista M.} and Siegfried, {Peter E.} and Kang, {Chang Jong} and Brown, {Craig M.} and Fu Chen and Lu Ma and Ehrlich, {Steven N.} and Yan Xin and Mark Croft and Wenqian Xu and Lapidus, {Saul H.} and Ghimire, {Nirmal J.} and Xiaoyan Tan",

note = "Funding Information: C.M.S., X.T., and N.J.G. were supported by the start-up funding from the George Mason University. C.-J.K. was supported by the NRF grant (NRF-2021R1F1A1063691). Use of the Advanced Photon Source at the Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. TEM work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. XANES work used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U. S. Department of Energy (DOE) Office of Science User Facility operated for DOE Office of Science by Brookhaven NationalLaboratory under Contract No.DE-SC0012704. Thesolid-state 500 MHz NMR spectrometer at the University of Maryland (UMD) was supported by the NSF MRI grant (NSF-1726058). The authors thank Dr. David Walker at the Columbia University for helping press the dense pellet. a Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

year = "2021",

month = nov,

day = "15",

doi = "10.1021/acs.inorgchem.1c02535",

language = "English (US)",

volume = "60",

pages = "17201--17211",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "22",

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TY - JOUR

T1 - Iridate Li8IrO6

T2 - An Antiferromagnetic Insulator

AU - Skaggs, Callista M.

AU - Siegfried, Peter E.

AU - Kang, Chang Jong

AU - Brown, Craig M.

AU - Chen, Fu

AU - Ma, Lu

AU - Ehrlich, Steven N.

AU - Xin, Yan

AU - Croft, Mark

AU - Xu, Wenqian

AU - Lapidus, Saul H.

AU - Ghimire, Nirmal J.

AU - Tan, Xiaoyan

N1 - Funding Information: C.M.S., X.T., and N.J.G. were supported by the start-up funding from the George Mason University. C.-J.K. was supported by the NRF grant (NRF-2021R1F1A1063691). Use of the Advanced Photon Source at the Argonne National Laboratory was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. TEM work was performed at the National High Magnetic Field Laboratory, which is supported by the National Science Foundation Cooperative Agreement No. DMR-1644779 and the State of Florida. XANES work used beamline 7-BM (QAS) of the National Synchrotron Light Source II, a U. S. Department of Energy (DOE) Office of Science User Facility operated for DOE Office of Science by Brookhaven NationalLaboratory under Contract No.DE-SC0012704. Thesolid-state 500 MHz NMR spectrometer at the University of Maryland (UMD) was supported by the NSF MRI grant (NSF-1726058). The authors thank Dr. David Walker at the Columbia University for helping press the dense pellet. a Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/11/15

Y1 - 2021/11/15

N2 - A polycrystalline iridate Li8IrO6 material was prepared via heating Li2O and IrO2 starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li8IrO6 adopts the nonpolar space group R3¯ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state 7Li NMR. This results in a crystal structure consisting of LiO4 tetrahedral layers alternating with mixed IrO6 and LiO6 octahedral layers along the crystallographic c-axis. The +4 oxidation state of Ir4+ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li8IrO6 indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a Néel temperature (TN) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment μeff (Ir) = 1.73 μB and insulating character indicate that Li8IrO6 is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.

AB - A polycrystalline iridate Li8IrO6 material was prepared via heating Li2O and IrO2 starting materials in a sealed quartz tube at 650 °C for 48 h. The structure was determined from Rietveld refinement of room-temperature powder neutron diffraction data. Li8IrO6 adopts the nonpolar space group R3¯ with Li atoms occupying the tetrahedral and octahedral sites, which is supported by the electron diffraction and solid-state 7Li NMR. This results in a crystal structure consisting of LiO4 tetrahedral layers alternating with mixed IrO6 and LiO6 octahedral layers along the crystallographic c-axis. The +4 oxidation state of Ir4+ was confirmed by near-edge X-ray absorption spectroscopy. An in situ synchrotron X-ray diffraction study of Li8IrO6 indicates that the sample is stable up to 1000 °C and exhibits no structural transitions. Magnetic measurements suggest long-range antiferromagnetic ordering with a Néel temperature (TN) of 4 K, which is corroborated by heat capacity measurements. The localized effective moment μeff (Ir) = 1.73 μB and insulating character indicate that Li8IrO6 is a correlated insulator. First-principles calculations support the nonpolar crystal structure and reveal the insulating behavior both in paramagnetic and antiferromagnetic states.

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DO - 10.1021/acs.inorgchem.1c02535

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SN - 0020-1669

VL - 60

SP - 17201

EP - 17211

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 22

ER -

Iridate Li₈IrO₆: An Antiferromagnetic Insulator

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