Low dimensionalization of magnetic ordering in $\mathrm{S}{\mathrm{r}}_{2}\mathrm{V}{\mathrm{O}}_{4}$ by hydride ion substitution

Low dimensionalization of magnetic ordering in $S r_{2} V O_{4}$ by hydride ion substitution

Joonho Bang, Satoru Matsuishi, Sachiko Maki, Jun-ichi Yamaura, Masatoshi Hiraishi, Soshi Takeshita, Ichihiro Yamauchi, Kenji M. Kojima, and Hideo Hosono

Phys. Rev. B 92, 064414 – Published 11 August 2015

Abstract

Substitution of an oxygen anion with a hydrogen anion induced the low dimensionalization of magnetic ordering in a transition metal oxide $S r_{2} V O_{4}$ . Upon increasing $x$ up to $\sim 1$ in $S r_{2} V O_{4 - x} H_{x}$ , the hydride ions were ordered linearly, and the magnetic susceptibility was simultaneously suppressed. It was found that this suppression was attributed to the formation of a quasi-one-dimensional antiferromagnetic spin chain, maintaining that each of the vanadium cations is two-dimensionally bridged by hydride and oxide ions. Density functional theory calculations demonstrate that the quasi-one-dimensional property is caused by much enhanced anisotropic exchange couplings $(J_{1} / J_{2} \sim 6)$ originating from the absence of $π$ bonding between $H 1 s$ and $V 3 d$ orbitals. Utilizing a hydride ion that has an ionic radius similar to an oxygen anion and only one energetically available orbital of $1 s$ is a different approach to realization of magnetic low dimensionalization in $3 d$ early transition metal oxides.

Received 28 January 2015
Revised 11 June 2015

DOI:https://doi.org/10.1103/PhysRevB.92.064414

Authors & Affiliations

Joonho Bang¹, Satoru Matsuishi², Sachiko Maki², Jun-ichi Yamaura², Masatoshi Hiraishi³, Soshi Takeshita³, Ichihiro Yamauchi³, Kenji M. Kojima³, and Hideo Hosono^1,2,4,*

¹Materials and Structures Laboratory, Tokyo Institute of Technology, Yokohama 226-8503, Japan
²Materials Research Center for Element Strategy, Tokyo Institute of Technology, Yokohama 226-8503, Japan
³Institute of Materials Structure Science, High Energy Accelerator Research Organization (KEK), Tsukuba, Ibaraki 305-0801, Japan
⁴Frontier Research Center, Tokyo Institute of Technology, Yokohama 226-8503, Japan

^*hosono@msl.titech.ac.jp

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Vol. 92, Iss. 6 — 1 August 2015

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Figure 1
Magnetic susceptibility and electrical resistivity of polycrystalline $S r_{2} V O_{4 - x} H_{x}$ as a function of $x$ . (a, b) Temperature-dependent magnetic susceptibility when $H = 7 T$ . The inset shows the zero-field cooled (ZFC) and field cooled (FC) magnetic susceptibilities for $x = 0.04$ and 1.00. (c) Temperature-dependent electrical resistivity data and their Arrhenius fit (red line) in the range 200–300 K. For $x > 0.50$ , the resistivity of each sample is beyond the range of our measurement system. (d) Electrical band gap $(E_{g})$ and effective magnetic moment $(μ_{eff})$ as a function of $x$ . Hydrogen anions statistically occupy each oxygen anion site in the low hydrogen substitution region $(x < 0.25)$ and are gradually ordered in the V-O plane with increasing hydrogen content, and a crystallographic transition (tetragonal to orthorhombic) occurs between $x = 0.50$ and 0.69.
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Figure 2
Low-dimensional behavior of $S r_{2} V O_{3} H$ . (a) Temperature-dependent magnetic susceptibility of $S r_{2} V O_{3} H (x = 1.00)$ in the high-temperature region. The red dashed curve shows the theoretical trace of the 1D-HAF spin-chain system including $3.4 %$ Curie-Weiss component $(χ_{CW})$ . The inset shows the temperature-dependent heat-capacity $(C_{p})$ data for $S r_{2} V O_{3} H$ with and without an external magnetic field (0 and 7 T). (b) Spin susceptibility $(χ_{spin})$ for $S r_{2} V O_{3} H$ (blue open circles) and the theoretical curves (dashed lines) of the $S = 1$ 1D-HAF spin-chain model for various exchange coupling constants $J$ . (c) Temperature-dependent muon spin oscillation frequencies $(ν)$ and nonmagnetic volume fraction $(f_{p})$ for $S r_{2} V O_{3} H$ . The inset shows zero-field and transverse-field time spectra of $S r_{2} V O_{3} H$ at various temperatures.
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Figure 3
Crystal structure and ordered spin states of $S r_{2} V O_{3} H$ . (a) Crystal structure of the anion-ordered layered oxyhydride $S r_{2} V O_{3} H$ . Note that the $H^{-}$ ions occupying $O^{2 -}$ sites are ordered linearly. The coordinate system for the DFT calculation is marked by blue arrows with $x, y$ , and $z$ . (b–e) Schematic representations of the four ordered spin states AFM1 (checkerboard), AFM2 (stripe), AFM3 (stripe), and FM of $S r_{2} V O_{3} H$ . $J_{1}, J_{2}$ , and $J_{3}$ indicate the exchange coupling constants through the V-O-V, V-H-V, and V-V interaction pathways, respectively.
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Figure 4
Calculated electronic structure of $S r_{2} V O_{3} H$ . (a–d) Total DOS and atomic PDOSs for the AFM1 model using MLWFs based on the results of a $GGA + U$ calculation with $U = 3.5 eV$ . The total DOS is the sum of the PDOSs of V, O, and H (excluding Sr). The direction along the V-H bond is set to the $z$ axis. (e, f) Schematic diagram of the orbital interaction to explain magnetic low dimensionalization by hydride ion substitution. Hydride ion substitution breaks the $π$ -exchange interaction between the $TM$ and an oxide ion.
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Physical Review B

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Low dimensionalization of magnetic ordering in $S r_{2} V O_{4}$ by hydride ion substitution

Joonho Bang, Satoru Matsuishi, Sachiko Maki, Jun-ichi Yamaura, Masatoshi Hiraishi, Soshi Takeshita, Ichihiro Yamauchi, Kenji M. Kojima, and Hideo Hosono

Phys. Rev. B 92, 064414 – Published 11 August 2015

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Low dimensionalization of magnetic ordering in Sr2VO4 by hydride ion substitution

Joonho Bang, Satoru Matsuishi, Sachiko Maki, Jun-ichi Yamaura, Masatoshi Hiraishi, Soshi Takeshita, Ichihiro Yamauchi, Kenji M. Kojima, and Hideo Hosono

Phys. Rev. B 92, 064414 – Published 11 August 2015

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Low dimensionalization of magnetic ordering in $S r_{2} V O_{4}$ by hydride ion substitution