Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides

Ningxin Jiang; Jinfei Zhou; Xue-Li Hao; Jingwei Li; Daliang Zhang; John Bacsa; Eun Sang Choi; Arun Ramanathan; Ryan E. Baumbach; Hong Li; Jean-Luc Bredas; Yu Han; Henry S. La Pierre

doi:10.1021/jacs.2c09633

Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides

Ningxin Jiang, Jinfei Zhou, Xue-Li Hao, Jingwei Li, Daliang Zhang, John Bacsa, Eun Sang Choi, Arun Ramanathan, Ryan E. Baumbach, Hong Li, Jean-Luc Bredas, Yu Han, Henry S. La Pierre

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

Abstract

Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH3NH3)2NaTi3F12, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH3NH3)2KTi3F12, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie–Weiss temperatures of both 1-Ti (−139.5(7) K) and 2-Ti (−83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.

Original language	English (US)
Journal	Journal of the American Chemical Society
DOIs	https://doi.org/10.1021/jacs.2c09633
State	Published - Dec 19 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-12-21
Acknowledgements: Studies were supported by the Beckman Foundation as part of a Beckman Young Investigator Award to H.S.L. Single-crystal diffraction experiment was performed at the Georgia Institute of Technology SCXRD facility directed by Dr. John Bacsa and established with funding from the Georgia Institute of Technology. This work was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (Grant ECCS-1542174). J.L.B. and H.L. acknowledge the support by the Army Research Office under Grant No. W911NF-17-1-0339; (2) X.L.H. acknowledges the support of China Scholarship Council (No. 201806170254). D.Z. thanks the National Key R&D Project of China (2022YFE0113800) and Thousand Talents Program for Distinguished Young Scholars. A portion of this 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.

ASJC Scopus subject areas

Biochemistry
Colloid and Surface Chemistry
General Chemistry
Catalysis

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10.1021/jacs.2c09633

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title = "Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides",

abstract = "Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH3NH3)2NaTi3F12, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH3NH3)2KTi3F12, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie–Weiss temperatures of both 1-Ti (−139.5(7) K) and 2-Ti (−83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.",

author = "Ningxin Jiang and Jinfei Zhou and Xue-Li Hao and Jingwei Li and Daliang Zhang and John Bacsa and Choi, {Eun Sang} and Arun Ramanathan and Baumbach, {Ryan E.} and Hong Li and Jean-Luc Bredas and Yu Han and {La Pierre}, {Henry S.}",

note = "KAUST Repository Item: Exported on 2022-12-21 Acknowledgements: Studies were supported by the Beckman Foundation as part of a Beckman Young Investigator Award to H.S.L. Single-crystal diffraction experiment was performed at the Georgia Institute of Technology SCXRD facility directed by Dr. John Bacsa and established with funding from the Georgia Institute of Technology. This work was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (Grant ECCS-1542174). J.L.B. and H.L. acknowledge the support by the Army Research Office under Grant No. W911NF-17-1-0339; (2) X.L.H. acknowledges the support of China Scholarship Council (No. 201806170254). D.Z. thanks the National Key R&D Project of China (2022YFE0113800) and Thousand Talents Program for Distinguished Young Scholars. A portion of this 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.",

year = "2022",

month = dec,

day = "19",

doi = "10.1021/jacs.2c09633",

language = "English (US)",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

}

TY - JOUR

T1 - Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides

AU - Jiang, Ningxin

AU - Zhou, Jinfei

AU - Hao, Xue-Li

AU - Li, Jingwei

AU - Zhang, Daliang

AU - Bacsa, John

AU - Choi, Eun Sang

AU - Ramanathan, Arun

AU - Baumbach, Ryan E.

AU - Li, Hong

AU - Bredas, Jean-Luc

AU - Han, Yu

AU - La Pierre, Henry S.

N1 - KAUST Repository Item: Exported on 2022-12-21 Acknowledgements: Studies were supported by the Beckman Foundation as part of a Beckman Young Investigator Award to H.S.L. Single-crystal diffraction experiment was performed at the Georgia Institute of Technology SCXRD facility directed by Dr. John Bacsa and established with funding from the Georgia Institute of Technology. This work was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (Grant ECCS-1542174). J.L.B. and H.L. acknowledge the support by the Army Research Office under Grant No. W911NF-17-1-0339; (2) X.L.H. acknowledges the support of China Scholarship Council (No. 201806170254). D.Z. thanks the National Key R&D Project of China (2022YFE0113800) and Thousand Talents Program for Distinguished Young Scholars. A portion of this 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.

PY - 2022/12/19

Y1 - 2022/12/19

N2 - Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH3NH3)2NaTi3F12, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH3NH3)2KTi3F12, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie–Weiss temperatures of both 1-Ti (−139.5(7) K) and 2-Ti (−83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.

AB - Many quantum magnetic materials suffer from structural imperfections. The effects of structural disorder on bulk properties are difficult to assess systematically from a chemical perspective due to the complexities of chemical synthesis. The recently reported S = 1/2 kagome lattice antiferromagnet, (CH3NH3)2NaTi3F12, 1-Ti, with highly symmetric kagome layers and disordered interlayer methylammonium cations, shows no magnetic ordering down to 0.1 K. To study the impact of structural disorder in the titanium fluoride kagome compounds, (CH3NH3)2KTi3F12, 2-Ti, was prepared. It presents no detectable structural disorder and only a small degree of distortion of the kagome lattice. The methylammonium disorder model of 1-Ti and order in 2-Ti were confirmed by atomic-resolution transmission electron microscopy. The antiferromagnetic interactions and band structures of both compounds were calculated based on spin-polarized density functional theory and support the magnetic structure analysis. Three spin-glass-like (SGL) transitions were observed in 2-Ti at 0.5, 1.4, and 2.3 K, while a single SGL transition can be observed in 1-Ti at 0.8 K. The absolute values of the Curie–Weiss temperatures of both 1-Ti (−139.5(7) K) and 2-Ti (−83.5(7) K) are larger than the SGL transition temperatures, which is indicative of geometrically frustrated spin glass (GFSG) states. All the SGL transitions are quenched with an applied field >0.1 T, which indicates novel magnetic phases emerge under small applied magnetic fields. The well-defined structure and the lack of structural disorder in 2-Ti suggest that 2-Ti is an ideal model compound for studying GFSG states and the potential transitions between spin liquid and GFSG states.

UR - http://hdl.handle.net/10754/686571

UR - https://pubs.acs.org/doi/abs/10.1021/jacs.2c09633

U2 - 10.1021/jacs.2c09633

DO - 10.1021/jacs.2c09633

M3 - Article

C2 - 36534963

SN - 0002-7863

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

ER -

Ground-State Spin Dynamics in d1 Kagome-Lattice Titanium Fluorides

Abstract

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