Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the LowTemperature Magnetic Properties of RInO_{3} (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between RareEarth Cations with Nonzero Orbital Moments
Abstract
Here, rareearth indium oxides RInO_{3} (R = Gd, Tb, Dy) consist of spinfrustrated hexagonal spin lattices made up of rareearth ions R^{3+}, where R^{3+} = Gd^{3+} (f^{7}, L = 0), Tb^{3+} (f^{8}, L = 3), and Dy^{3+} (f^{9}, L = 5). We carried out DFT calculations for RInO_{3}, including onsite repulsion U with/without spin–orbit coupling (SOC), to explore if their lowtemperature magnetic properties are related to the two nonequivalent nearestneighbor (NN) spin exchanges of their hexagonal spin lattices. Our DFT + U + SOC calculations predict that the orbital moments of the Tb^{3+} and Dy^{3+} ions are smaller than their freeion values by ~2μ_{B} while the Tb^{3+} spins have an inplane magnetic anisotropy, in agreement with the experiments. This suggests that the f orbitals of each R^{3+} (R = Tb, Dy) ion are engaged, though weakly, in bonding with the surrounding ligand atoms. The magnetic properties of GdInO_{3} with the zero orbital moment are adequately described by the spin exchanges extracted by DFT + U calculations. In describing the magnetic properties of TbInO_{3} and DyInO_{3} with nonzero orbital moments, however, the spin exchanges extracted by DFT + U + SOC calculations are necessary.
 Authors:

 North Carolina State Univ., Raleigh, NC (United States)
 Chinese Academy of Sciences (CAS), Fuzhou (China)
 Rutgers Univ., Piscataway, NJ (United States)
 North Carolina State Univ., Raleigh, NC (United States); Chinese Academy of Sciences (CAS), Fuzhou (China)
 Publication Date:
 Research Org.:
 Rutgers Univ., Piscataway, NJ (United States)
 Sponsoring Org.:
 USDOE
 OSTI Identifier:
 1461270
 Grant/Contract Number:
 FG0207ER46382
 Resource Type:
 Accepted Manuscript
 Journal Name:
 Inorganic Chemistry
 Additional Journal Information:
 Journal Volume: 57; Journal Issue: 15; Journal ID: ISSN 00201669
 Publisher:
 American Chemical Society (ACS)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
Citation Formats
Gordon, Elijah E., Cheng, Xiyue, Kim, Jaewook, Cheong, Sang Wook, Deng, Shuiquan, and Whangbo, Myung Hwan. Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the LowTemperature Magnetic Properties of RInO3 (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between RareEarth Cations with Nonzero Orbital Moments. United States: N. p., 2018.
Web. doi:10.1021/acs.inorgchem.8b01274.
Gordon, Elijah E., Cheng, Xiyue, Kim, Jaewook, Cheong, Sang Wook, Deng, Shuiquan, & Whangbo, Myung Hwan. Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the LowTemperature Magnetic Properties of RInO3 (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between RareEarth Cations with Nonzero Orbital Moments. United States. https://doi.org/10.1021/acs.inorgchem.8b01274
Gordon, Elijah E., Cheng, Xiyue, Kim, Jaewook, Cheong, Sang Wook, Deng, Shuiquan, and Whangbo, Myung Hwan. Mon .
"Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the LowTemperature Magnetic Properties of RInO3 (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between RareEarth Cations with Nonzero Orbital Moments". United States. https://doi.org/10.1021/acs.inorgchem.8b01274. https://www.osti.gov/servlets/purl/1461270.
@article{osti_1461270,
title = {Nonequivalent Spin Exchanges of the Hexagonal Spin Lattice Affecting the LowTemperature Magnetic Properties of RInO3 (R = Gd, Tb, Dy): Importance of Spin–Orbit Coupling for Spin Exchanges between RareEarth Cations with Nonzero Orbital Moments},
author = {Gordon, Elijah E. and Cheng, Xiyue and Kim, Jaewook and Cheong, Sang Wook and Deng, Shuiquan and Whangbo, Myung Hwan},
abstractNote = {Here, rareearth indium oxides RInO3 (R = Gd, Tb, Dy) consist of spinfrustrated hexagonal spin lattices made up of rareearth ions R3+, where R3+ = Gd3+ (f7, L = 0), Tb3+ (f8, L = 3), and Dy3+ (f9, L = 5). We carried out DFT calculations for RInO3, including onsite repulsion U with/without spin–orbit coupling (SOC), to explore if their lowtemperature magnetic properties are related to the two nonequivalent nearestneighbor (NN) spin exchanges of their hexagonal spin lattices. Our DFT + U + SOC calculations predict that the orbital moments of the Tb3+ and Dy3+ ions are smaller than their freeion values by ~2μB while the Tb3+ spins have an inplane magnetic anisotropy, in agreement with the experiments. This suggests that the f orbitals of each R3+ (R = Tb, Dy) ion are engaged, though weakly, in bonding with the surrounding ligand atoms. The magnetic properties of GdInO3 with the zero orbital moment are adequately described by the spin exchanges extracted by DFT + U calculations. In describing the magnetic properties of TbInO3 and DyInO3 with nonzero orbital moments, however, the spin exchanges extracted by DFT + U + SOC calculations are necessary.},
doi = {10.1021/acs.inorgchem.8b01274},
journal = {Inorganic Chemistry},
number = 15,
volume = 57,
place = {United States},
year = {2018},
month = {7}
}
Web of Science
Figures / Tables:
Works referenced in this record:
Evolution of lattice dynamics in ferroelectric hexagonal REInO _{3} (RE = Ho, Dy, Tb, Gd, Eu, Sm) perovskites
journal, July 2016
 Paul, Barnita; Chatterjee, Swastika; Gop, Sumana
 Materials Research Express, Vol. 3, Issue 7
Geometric ferroelectricity in rareearth compounds $R{\text{GaO}}_{3}$ and $R{\text{InO}}_{3}$
journal, April 2009
 Tohei, Tetsuya; Moriwake, Hiroki; Murata, Hidenobu
 Physical Review B, Vol. 79, Issue 14
Geometrically frustrated magnetic materials
journal, January 2001
 Greedan, John E.
 Journal of Materials Chemistry, Vol. 11, Issue 1
Geometrically frustrated ${\mathrm{GdInO}}_{3}$ : An exotic system to study negative thermal expansion and spinlattice coupling
journal, February 2017
 Paul, Barnita; Chatterjee, Swastika; Roy, Anushree
 Physical Review B, Vol. 95, Issue 5
Magnetochromic effect in multiferroic $R{\mathrm{In}}_{1x}{\mathrm{Mn}}_{x}{\mathrm{O}}_{3}$ ( $R=\mathrm{Tb}$ , Dy)
journal, May 2015
 Chen, P.; Holinsworth, B. S.; O'Neal, K. R.
 Physical Review B, Vol. 91, Issue 20
Magnetic properties and energymapping analysis
journal, January 2013
 Xiang, Hongjun; Lee, Changhoon; Koo, HyunJoo
 Dalton Trans., Vol. 42, Issue 4
Efficient iterative schemes for ab initio totalenergy calculations using a planewave basis set
journal, October 1996
 Kresse, G.; Furthmüller, J.
 Physical Review B, Vol. 54, Issue 16, p. 1116911186
Efficiency of abinitio total energy calculations for metals and semiconductors using a planewave basis set
journal, July 1996
 Kresse, G.; Furthmüller, J.
 Computational Materials Science, Vol. 6, Issue 1, p. 1550
Projector augmentedwave method
journal, December 1994
 Blöchl, P. E.
 Physical Review B, Vol. 50, Issue 24, p. 1795317979
From ultrasoft pseudopotentials to the projector augmentedwave method
journal, January 1999
 Kresse, G.; Joubert, D.
 Physical Review B, Vol. 59, Issue 3, p. 17581775
Generalized Gradient Approximation Made Simple
journal, October 1996
 Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
 Physical Review Letters, Vol. 77, Issue 18, p. 38653868
Electronenergyloss 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. 15051509
Electronic structure of fcc Th: Spinorbit calculation with ${6p}_{1/2}$ local orbital extension
journal, September 2001
 Kuneš, J.; Novák, P.; Schmid, R.
 Physical Review B, Vol. 64, Issue 15
Prediction of Spin Orientations in Terms of HOMO–LUMO Interactions Using Spin–Orbit Coupling as Perturbation
journal, November 2015
 Whangbo, MyungHwan; Gordon, Elijah E.; Xiang, Hongjun
 Accounts of Chemical Research, Vol. 48, Issue 12
Spin orientations of the spinhalf Ir ^{4+} ions in Sr _{3} NiIrO _{6} , Sr _{2} IrO _{4} , and Na _{2} IrO _{3} : Density functional, perturbation theory, and Madelung potential analyses
journal, March 2016
 Gordon, Elijah E.; Xiang, Hongjun; Köhler, Jürgen
 The Journal of Chemical Physics, Vol. 144, Issue 11
Analysis of the Uniaxial Magnetic Properties of HighSpin d ^{6} Ions at Trigonal Prism and Linear TwoCoordinate Sites: Uniaxial Magnetic Properties of Ca _{3} Co _{2} O _{6} and Fe[C(SiMe _{3} ) _{3} ] _{2}
journal, June 2005
 Dai, Dadi; Whangbo, MyungHwan
 Inorganic Chemistry, Vol. 44, Issue 12
Effective Field Theories of Magnetism
journal, August 1966
 Smart, J. Samuel; Van Vleck, J. H.
 Physics Today, Vol. 19, Issue 8
Works referencing / citing this record:
Spin Liquid State and Topological Structural Defects in Hexagonal ${\mathrm{TbInO}}_{3}$
journal, July 2019
 Kim, Jaewook; Wang, Xueyun; Huang, FeiTing
 Physical Review X, Vol. 9, Issue 3
REZnAl _{11} O _{19} (RE = Pr, Nd, Sm–Tb): a new family of ideal 2D triangular lattice frustrated magnets
journal, January 2019
 Ashtar, M.; Marwat, M. A.; Gao, Y. X.
 Journal of Materials Chemistry C, Vol. 7, Issue 32
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