Experimental and computational studies on solvent-free rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd)

Toyoto Sato, Kazutoshi Miwa, Yuko Nakamori, Kenji Ohoyama, Hai Wen Li, Tatsuo Noritake, Masakazu Aoki, Shin Ichi Towata, Shin Ichi Orimo

Research output: Contribution to journalArticle

91 Citations (Scopus)

Abstract

Solvent-free trivalent rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd) were synthesized from R Cl3 and LiB H4 through solid-state metathesis reactions and characterized by powder x-ray or neutron diffraction measurement and Raman spectroscopy combined with first-principles calculations. The crystal structure of R (B H4) 3 was clarified to adopt a primitive cubic structure with Y (B H4) 3: a=10.852 (1), Dy (B H4) 3: a=10.885 (3), and Gd (B H4) 3: a=10.983 (5) in space group Pa 3̄ (No. 205), the [B H4] - complex anions of which locate on the edges of a distorted cube composed of R3+. Based on the crystal structure, the observed Raman scattering positions are theoretically assigned such that the B H4 bending is at 1050-1300 cm-1 and B H4 stretching is at 2250-2400 cm-1, respectively. In addition, the computational studies on Y (B H4) 3 suggested it to be an insulator that occupied B 2s,2p and H 1s orbitals with little contribution from Y, and the heat of formation was ΔH=-113 kJ mol B H4, which was estimated from (13) Y+B+2 H2 → (13) Y (B H4) 3.

Original languageEnglish
Article number104114
JournalPhysical Review B - Condensed Matter and Materials Physics
Volume77
Issue number10
DOIs
Publication statusPublished - Mar 17 2008

Fingerprint

Rare Earth Metals
Borohydrides
borohydrides
Rare earths
rare earth elements
Crystal structure
crystal structure
metathesis
heat of formation
Neutron diffraction
Metals
Solid state reactions
Powders
metals
Stretching
Anions
neutron diffraction
Raman spectroscopy
Raman scattering
x ray diffraction

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Condensed Matter Physics

Cite this

Experimental and computational studies on solvent-free rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd). / Sato, Toyoto; Miwa, Kazutoshi; Nakamori, Yuko; Ohoyama, Kenji; Li, Hai Wen; Noritake, Tatsuo; Aoki, Masakazu; Towata, Shin Ichi; Orimo, Shin Ichi.

In: Physical Review B - Condensed Matter and Materials Physics, Vol. 77, No. 10, 104114, 17.03.2008.

Research output: Contribution to journalArticle

Sato, Toyoto ; Miwa, Kazutoshi ; Nakamori, Yuko ; Ohoyama, Kenji ; Li, Hai Wen ; Noritake, Tatsuo ; Aoki, Masakazu ; Towata, Shin Ichi ; Orimo, Shin Ichi. / Experimental and computational studies on solvent-free rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd). In: Physical Review B - Condensed Matter and Materials Physics. 2008 ; Vol. 77, No. 10.
@article{e1d8b19e3df24c5e891f858d15723bbc,
title = "Experimental and computational studies on solvent-free rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd)",
abstract = "Solvent-free trivalent rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd) were synthesized from R Cl3 and LiB H4 through solid-state metathesis reactions and characterized by powder x-ray or neutron diffraction measurement and Raman spectroscopy combined with first-principles calculations. The crystal structure of R (B H4) 3 was clarified to adopt a primitive cubic structure with Y (B H4) 3: a=10.852 (1), Dy (B H4) 3: a=10.885 (3), and Gd (B H4) 3: a=10.983 (5) in space group Pa 3̄ (No. 205), the [B H4] - complex anions of which locate on the edges of a distorted cube composed of R3+. Based on the crystal structure, the observed Raman scattering positions are theoretically assigned such that the B H4 bending is at 1050-1300 cm-1 and B H4 stretching is at 2250-2400 cm-1, respectively. In addition, the computational studies on Y (B H4) 3 suggested it to be an insulator that occupied B 2s,2p and H 1s orbitals with little contribution from Y, and the heat of formation was ΔH=-113 kJ mol B H4, which was estimated from (13) Y+B+2 H2 → (13) Y (B H4) 3.",
author = "Toyoto Sato and Kazutoshi Miwa and Yuko Nakamori and Kenji Ohoyama and Li, {Hai Wen} and Tatsuo Noritake and Masakazu Aoki and Towata, {Shin Ichi} and Orimo, {Shin Ichi}",
year = "2008",
month = "3",
day = "17",
doi = "10.1103/PhysRevB.77.104114",
language = "English",
volume = "77",
journal = "Physical Review B - Condensed Matter and Materials Physics",
issn = "1098-0121",
publisher = "American Physical Society",
number = "10",

}

TY - JOUR

T1 - Experimental and computational studies on solvent-free rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd)

AU - Sato, Toyoto

AU - Miwa, Kazutoshi

AU - Nakamori, Yuko

AU - Ohoyama, Kenji

AU - Li, Hai Wen

AU - Noritake, Tatsuo

AU - Aoki, Masakazu

AU - Towata, Shin Ichi

AU - Orimo, Shin Ichi

PY - 2008/3/17

Y1 - 2008/3/17

N2 - Solvent-free trivalent rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd) were synthesized from R Cl3 and LiB H4 through solid-state metathesis reactions and characterized by powder x-ray or neutron diffraction measurement and Raman spectroscopy combined with first-principles calculations. The crystal structure of R (B H4) 3 was clarified to adopt a primitive cubic structure with Y (B H4) 3: a=10.852 (1), Dy (B H4) 3: a=10.885 (3), and Gd (B H4) 3: a=10.983 (5) in space group Pa 3̄ (No. 205), the [B H4] - complex anions of which locate on the edges of a distorted cube composed of R3+. Based on the crystal structure, the observed Raman scattering positions are theoretically assigned such that the B H4 bending is at 1050-1300 cm-1 and B H4 stretching is at 2250-2400 cm-1, respectively. In addition, the computational studies on Y (B H4) 3 suggested it to be an insulator that occupied B 2s,2p and H 1s orbitals with little contribution from Y, and the heat of formation was ΔH=-113 kJ mol B H4, which was estimated from (13) Y+B+2 H2 → (13) Y (B H4) 3.

AB - Solvent-free trivalent rare-earth metal borohydrides R (B H4) 3 (R=Y, Dy, and Gd) were synthesized from R Cl3 and LiB H4 through solid-state metathesis reactions and characterized by powder x-ray or neutron diffraction measurement and Raman spectroscopy combined with first-principles calculations. The crystal structure of R (B H4) 3 was clarified to adopt a primitive cubic structure with Y (B H4) 3: a=10.852 (1), Dy (B H4) 3: a=10.885 (3), and Gd (B H4) 3: a=10.983 (5) in space group Pa 3̄ (No. 205), the [B H4] - complex anions of which locate on the edges of a distorted cube composed of R3+. Based on the crystal structure, the observed Raman scattering positions are theoretically assigned such that the B H4 bending is at 1050-1300 cm-1 and B H4 stretching is at 2250-2400 cm-1, respectively. In addition, the computational studies on Y (B H4) 3 suggested it to be an insulator that occupied B 2s,2p and H 1s orbitals with little contribution from Y, and the heat of formation was ΔH=-113 kJ mol B H4, which was estimated from (13) Y+B+2 H2 → (13) Y (B H4) 3.

UR - http://www.scopus.com/inward/record.url?scp=41549150217&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=41549150217&partnerID=8YFLogxK

U2 - 10.1103/PhysRevB.77.104114

DO - 10.1103/PhysRevB.77.104114

M3 - Article

AN - SCOPUS:41549150217

VL - 77

JO - Physical Review B - Condensed Matter and Materials Physics

JF - Physical Review B - Condensed Matter and Materials Physics

SN - 1098-0121

IS - 10

M1 - 104114

ER -