skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba 3Ln 2O 5Cl 2

Abstract

Single crystals of a new family of layered lanthanide oxychlorides, Ba 3Ln 2O 5Cl 2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.

Authors:
ORCiD logo [1];  [2];  [3];  [2];  [4];  [4];  [2];  [3];  [5]
  1. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Missouri State Univ., Springfield, MO (United States). Dept. of Physics, Astronomy, and Materials Science
  2. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab)
  3. Univ. of Missouri, Columbia, MO (United States). Dept. of Physics and Astronomy
  4. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Florida State Univ., Tallahassee, FL (United States). Dept. of Physics
  5. Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab. (MagLab); Florida State Univ., Tallahassee, FL (United States), FAMU-FSU College of Engineering, Dept. of Chemical and Biomedical Engineering
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Solid-State Solar-Thermal Energy Conversion Center (S3TEC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470520
Grant/Contract Number:  
[SC0001299; FG02-09ER46577; SC0008832]
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
[ Journal Volume: 57; Journal Issue: 4; Related Information: S3TEC partners with Massachusetts Institute of Technology (lead); Boston College; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute]; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; solar (photovoltaic); solar (thermal); solid state lighting; phonons; thermal conductivity; thermoelectric; defects; mechanical behavior; charge transport; spin dynamics; materials and chemistry by design; optics; synthesis (novel materials); synthesis (self-assembly); synthesis (scalable processing)

Citation Formats

Besara, Tiglet, Ramirez, Daniel C., Sun, Jifeng, Falb, Nathaniel W., Lan, Wangwei, Neu, Jennifer N., Whalen, Jeffrey B., Singh, David J., and Siegrist, Theo. Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2. United States: N. p., 2018. Web. doi:10.1021/acs.inorgchem.7b02265.
Besara, Tiglet, Ramirez, Daniel C., Sun, Jifeng, Falb, Nathaniel W., Lan, Wangwei, Neu, Jennifer N., Whalen, Jeffrey B., Singh, David J., & Siegrist, Theo. Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2. United States. doi:10.1021/acs.inorgchem.7b02265.
Besara, Tiglet, Ramirez, Daniel C., Sun, Jifeng, Falb, Nathaniel W., Lan, Wangwei, Neu, Jennifer N., Whalen, Jeffrey B., Singh, David J., and Siegrist, Theo. Fri . "Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2". United States. doi:10.1021/acs.inorgchem.7b02265. https://www.osti.gov/servlets/purl/1470520.
@article{osti_1470520,
title = {Synthesis and Crystal Structure of the Layered Lanthanide Oxychlorides Ba3Ln2O5Cl2},
author = {Besara, Tiglet and Ramirez, Daniel C. and Sun, Jifeng and Falb, Nathaniel W. and Lan, Wangwei and Neu, Jennifer N. and Whalen, Jeffrey B. and Singh, David J. and Siegrist, Theo},
abstractNote = {Single crystals of a new family of layered lanthanide oxychlorides, Ba3Ln2O5Cl2 (Ln = Gd–Lu), have been synthesized from a molten barium flux. This family crystallizes in the space group I4/mmm (No. 139; Z = 2) with lattice parameters a = 4.3384(1)–4.4541(1) Å and c = 24.5108(7)–24.8448(9) Å. Ba3Ln2O5Cl2 phases are built up of two different blocks: a perovskite double layer of stoichiometry Ba2Ln2O5 formed by corner-connected LnO5 tetragonal bipyramids and a puckered rock-salt-like interlayer of composition BaCl2. A complete structural study along with bond-valence-sum calculations shows that, for lanthanides larger than gadolinium, the structure becomes unstable. Density functional theory calculations show that the valence-band edge is dominated by oxygen orbitals, whereas the conduction band forms from Ba 5d orbitals. Finally, the synthesis of this family suggests a route to other potential multianion phases.},
doi = {10.1021/acs.inorgchem.7b02265},
journal = {Inorganic Chemistry},
number = [4],
volume = [57],
place = {United States},
year = {2018},
month = {2}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share: