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Title: Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior

In a new series of transition metal vanadates, namely, Ba 2M(VO 4) 2(OH) (M = V 3+, Mn 3+, and Fe 3+), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 °C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba 2V(VO 4) 2(OH) is monoclinic in space group P2 1/m, a = 7.8783(2) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å 3. Moreover, the other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba 2Mn(VO 4) 2(OH) analogue yielded a new understanding of the Jahn–Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Finally, single-crystal temperature-dependent magnetic studies on Ba 2V(VO 4) 2(OH) reveal a broad feature over a wide temperature range with maximum at ~100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetismmore » studies.« less
Authors:
 [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [1] ;  [1]
  1. Clemson Univ., SC (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Publication Date:
Grant/Contract Number:
AC05-00OR22725
Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 54; Journal Issue: 14; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Research Org:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org:
USDOE Office of Science (SC); National Science Foundation (NSF)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1265840

Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., and Kolis, Joseph W.. Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior. United States: N. p., Web. doi:10.1021/acs.inorgchem.5b01037.
Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., & Kolis, Joseph W.. Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior. United States. doi:10.1021/acs.inorgchem.5b01037.
Sanjeewa, Liurukara D., McGuire, Michael A., Garlea, Vasile O., Hu, Longyu, Chumanov, George, McMillen, Colin D., and Kolis, Joseph W.. 2015. "Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior". United States. doi:10.1021/acs.inorgchem.5b01037. https://www.osti.gov/servlets/purl/1265840.
@article{osti_1265840,
title = {Hydrothermal Synthesis and Characterization of Novel Brackebuschite-Type Transition Metal Vanadates: Ba 2 M(VO 4 ) 2 (OH), M = V 3+ , Mn 3+ , and Fe 3+ , with Interesting Jahn–Teller and Spin-Liquid Behavior},
author = {Sanjeewa, Liurukara D. and McGuire, Michael A. and Garlea, Vasile O. and Hu, Longyu and Chumanov, George and McMillen, Colin D. and Kolis, Joseph W.},
abstractNote = {In a new series of transition metal vanadates, namely, Ba2M(VO4)2(OH) (M = V3+, Mn3+, and Fe3+), was synthesized as large single crystals hydrothermally in 5 M NaOH solution at 580 °C and 1 kbar. This new series of compounds is structurally reminiscent of the brackebuschite mineral type. The structure of Ba2V(VO4)2(OH) is monoclinic in space group P21/m, a = 7.8783(2) Å, b = 6.1369(1) Å, c = 9.1836(2) Å, β = 113.07(3)°, V = 408.51(2) Å3. Moreover, the other structures are similar and consist of one-dimensional trans edge-shared distorted octahedral chains running along the b-axis. The vanadate groups bridge across edges of their tetrahedra. Structural analysis of the Ba2Mn(VO4)2(OH) analogue yielded a new understanding of the Jahn–Teller effect in this structure type. Raman and infrared spectra were investigated to observe the fundamental vanadate and hydroxide vibrational modes. Finally, single-crystal temperature-dependent magnetic studies on Ba2V(VO4)2(OH) reveal a broad feature over a wide temperature range with maximum at ~100 K indicating that an energy gap could exist between the antiferromagnetic singlet ground state and excited triplet states, making it potentially of interest for quantum magnetism studies.},
doi = {10.1021/acs.inorgchem.5b01037},
journal = {Inorganic Chemistry},
number = 14,
volume = 54,
place = {United States},
year = {2015},
month = {7}
}