Oxygen trapped by rare earth tetrahedral clusters in Nd{sub 4}FeOS{sub 6}: Crystal structure, electronic structure, and magnetic properties

Journal Article · Tue Sep 15 00:00:00 EDT 2015 · Journal of Solid State Chemistry

DOI:https://doi.org/10.1016/J.JSSC.2015.05.020· OSTI ID:22486751

Lin, Qisheng ^[1]; Taufour, Valentin ^[1]; Zhang, Yuemei ^[2]; Wood, Max; Drtina, Thomas; Bud’ko, Sergey L.; Canfield, Paul C. ^[1]; Miller, Gordon J. ^[1]

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1. Division of Materials Sciences and Engineering, Ames Laboratory, US-DOE, Ames, IA 50011 (United States)
2. Department of Chemistry, Iowa State University, Ames, IA 50011 (United States)

Single crystals of Nd{sub 4}FeOS{sub 6} were grown from an Fe–S eutectic solution. Single crystal X-ray diffraction analysis revealed a Nd{sub 4}MnOSe{sub 6}-type structure (P6{sub 3}mc, a=9.2693(1) Å, c=6.6650(1)Å, V=495.94(1) Å{sup 3}, Z=2), featuring parallel chains of face-sharing [FeS{sub 6×1/2}]{sup 4−} trigonal antiprisms and interlinked [Nd{sub 4}OS{sub 3}]{sup 4+} cubane-like clusters. Oxygen atoms were found to be trapped by Nd{sub 4} clusters in the [Nd{sub 4}OS{sub 3}]{sup 4{sub +}} chains. Structural differences among Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6} and the related La{sub 3}CuSiS{sub 7}− and Pr{sub 8}CoGa{sub 3}-type structures have been described. Magnetic susceptibility measurements on Nd{sub 4}FeOS{sub 6} suggested the dominance of antiferromagnetic interactions at low temperature, but no magnetic ordering down to 2 K was observed. Spin-polarized electronic structure calculations revealed magnetic frustration with dominant antiferromagnetic interactions. - Graphical abstract: Trapping of oxygen in Nd{sub 4} tetrahedral clusters results in the formation of the Nd{sub 4}MnOSe{sub 6}-type Nd{sub 4}FeOS{sub 6}, in contrast to the La{sub 3}CuSiS{sub 7}-type oxygen-free Nd{sub 4}FeS{sub 7} and related Pr{sub 8}CoGa{sub 3}-type structures. Complex magnetic frustration inhibits magnetic ordering at low temperature. - Highlights: • Single crystals of Nd{sub 4}FeOS{sub 6} were grown using self-flux method. • Oxygen was found trapped by Nd{sub 4} tetrahedral clusters. • Comparison with two closely related structural types were discussed. • Magnetic measurements revealed antiferromagnetic (AFM) interaction. • VASP calculations confirmed strong magnetic frustration in AFM model.

• OSTI ID: 22486751
• Journal Information: Journal of Solid State Chemistry, Vol. 229; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); ISSN 0022-4596
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ANTIFERROMAGNETISM
ATOMIC FORCE MICROSCOPY
COMPARATIVE EVALUATIONS
COPPER SILICIDES
COPPER SULFIDES
CRYSTAL GROWTH
CRYSTAL STRUCTURE
DEUTERIDES
ELECTRONIC STRUCTURE
EUTECTICS
HEXAGONAL LATTICES
IRON OXIDES
IRON SULFIDES
LANTHANUM COMPOUNDS
MAGNETIC SUSCEPTIBILITY
MAGNETIZATION
MONOCRYSTALS
NEODYMIUM COMPOUNDS
SPIN ORIENTATION
X-RAY DIFFRACTION