Crystal and electronic structure and magnetic properties of divalent europium perovskite oxides Eu M O 3 (M = Ti, Zr, and Hf): Experimental and first-principles approaches

Hirofumi Akamatsu, Koji Fujita, Hiroyuki Hayashi, Takahiro Kawamoto, Yu Kumagai, Yanhua Zong, Koji Iwata, Fumiyasu Oba, Isao Tanaka, Katsuhisa Tanaka

Research output: Contribution to journalArticle

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Abstract

A comparative study of the crystal and electronic structure and magnetism of divalent europium perovskite oxides EuMO 3 (M = Ti, Zr, and Hf) has been performed on the basis of both experimental and theoretical approaches playing complementary roles. The compounds were synthesized via solid-state reactions. EuZrO 3 and EuHfO 3 have an orthorhombic structure with a space group Pbnm at room temperature contrary to EuTiO 3, which is cubic at room temperature. The optical band gaps of EuZrO 3 and EuHfO 3 are found to be about 2.4 and 2.7 eV, respectively, much larger than that of EuTiO 3 (0.8 eV). On the other hand, the present compounds exhibit similar magnetic properties characterized by paramagnetic-antiferromagnetic transitions at around 5 K, spin flop at moderate magnetic fields lower than 1 T, and the antiferromagnetic nearest-neighbor and ferromagnetic next-nearest-neighbor exchange interactions. First-principles calculations based on a hybrid Hartree-Fock density functional approach yield lattice constants, band gaps, and magnetic interactions in good agreement with those obtained experimentally. The band gap excitations are assigned to electronic transitions from the Eu 4f to Mnd states for EuMO 3 (M = Ti, Zr, and Hf and n = 3, 4, and 5, respectively).

Original languageEnglish
Pages (from-to)4560-4567
Number of pages8
JournalInorganic chemistry
Volume51
Issue number8
DOIs
Publication statusPublished - Apr 16 2012
Externally publishedYes

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Europium
europium
Oxides
Electronic structure
Magnetic properties
Energy gap
Crystal structure
electronic structure
magnetic properties
crystal structure
oxides
Exchange interactions
Optical band gaps
Magnetism
Electron transitions
Solid state reactions
Lattice constants
room temperature
Magnetic fields
Temperature

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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Crystal and electronic structure and magnetic properties of divalent europium perovskite oxides Eu M O 3 (M = Ti, Zr, and Hf) : Experimental and first-principles approaches. / Akamatsu, Hirofumi; Fujita, Koji; Hayashi, Hiroyuki; Kawamoto, Takahiro; Kumagai, Yu; Zong, Yanhua; Iwata, Koji; Oba, Fumiyasu; Tanaka, Isao; Tanaka, Katsuhisa.

In: Inorganic chemistry, Vol. 51, No. 8, 16.04.2012, p. 4560-4567.

Research output: Contribution to journalArticle

Akamatsu, Hirofumi ; Fujita, Koji ; Hayashi, Hiroyuki ; Kawamoto, Takahiro ; Kumagai, Yu ; Zong, Yanhua ; Iwata, Koji ; Oba, Fumiyasu ; Tanaka, Isao ; Tanaka, Katsuhisa. / Crystal and electronic structure and magnetic properties of divalent europium perovskite oxides Eu M O 3 (M = Ti, Zr, and Hf) : Experimental and first-principles approaches. In: Inorganic chemistry. 2012 ; Vol. 51, No. 8. pp. 4560-4567.
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abstract = "A comparative study of the crystal and electronic structure and magnetism of divalent europium perovskite oxides EuMO 3 (M = Ti, Zr, and Hf) has been performed on the basis of both experimental and theoretical approaches playing complementary roles. The compounds were synthesized via solid-state reactions. EuZrO 3 and EuHfO 3 have an orthorhombic structure with a space group Pbnm at room temperature contrary to EuTiO 3, which is cubic at room temperature. The optical band gaps of EuZrO 3 and EuHfO 3 are found to be about 2.4 and 2.7 eV, respectively, much larger than that of EuTiO 3 (0.8 eV). On the other hand, the present compounds exhibit similar magnetic properties characterized by paramagnetic-antiferromagnetic transitions at around 5 K, spin flop at moderate magnetic fields lower than 1 T, and the antiferromagnetic nearest-neighbor and ferromagnetic next-nearest-neighbor exchange interactions. First-principles calculations based on a hybrid Hartree-Fock density functional approach yield lattice constants, band gaps, and magnetic interactions in good agreement with those obtained experimentally. The band gap excitations are assigned to electronic transitions from the Eu 4f to Mnd states for EuMO 3 (M = Ti, Zr, and Hf and n = 3, 4, and 5, respectively).",
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