A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units
Abstract
Here we carried out a detailed structural study of the family of rare earth molybdenum bronzes, and synthesized reduced ternary molybdates of composition LnMo16O44. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO3-type Mo8O36 structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μB moments on each Mo. We suggest that the Mo8O36 units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, willmore »
- Authors:
-
[2];
- Montclair State Univ., Montclair, NJ (United States)
- FAMU-FSU College of Engineering, Tallahassee, FL (United States); National High Magnetic Field Lab., Tallahassee, FL (United States)
- National High Magnetic Field Lab., Tallahassee, FL (United States)
- FAMU-FSU College of Engineering, Tallahassee, FL (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Publication Date:
- Research Org.:
- Florida State Univ., Tallahassee, FL (United States); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Contributing Org.:
- Oak Ridge National Laboratory; Montclair State University
- OSTI Identifier:
- 1333511
- Alternate Identifier(s):
- OSTI ID: 1253042; OSTI ID: 1265478
- Grant/Contract Number:
- SC0008832; AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Solid State Chemistry
- Additional Journal Information:
- Journal Volume: 227; Journal Issue: C; Journal ID: ISSN 0022-4596
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; molybdenum bronzes; crystallographic structure; magnetism; Mo8O36 units; DFT calculations
Citation Formats
Schneemeyer, L. F., Siegrist, T., Besara, T., Lundberg, M., Sun, J., and Singh, D. J. A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units. United States: N. p., 2015.
Web. doi:10.1016/j.jssc.2015.03.028.
Schneemeyer, L. F., Siegrist, T., Besara, T., Lundberg, M., Sun, J., & Singh, D. J. A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units. United States. https://doi.org/10.1016/j.jssc.2015.03.028
Schneemeyer, L. F., Siegrist, T., Besara, T., Lundberg, M., Sun, J., and Singh, D. J. Mon .
"A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units". United States. https://doi.org/10.1016/j.jssc.2015.03.028. https://www.osti.gov/servlets/purl/1333511.
@article{osti_1333511,
title = {A family of rare earth molybdenum bronzes: Oxides consisting of periodic arrays of interacting magnetic units},
author = {Schneemeyer, L. F. and Siegrist, T. and Besara, T. and Lundberg, M. and Sun, J. and Singh, D. J.},
abstractNote = {Here we carried out a detailed structural study of the family of rare earth molybdenum bronzes, and synthesized reduced ternary molybdates of composition LnMo16O44. Bond valence sum (BVS) calculations clearly show that the molybdenum ions in tetrahedral coordination are hexavalent while the electron count in the primitive unit cell is odd. Yet, measurements show that the phases are semiconductors. The temperature dependence of the magnetic susceptibility of samples containing several different rare earth elements was measured. These measurements verified the presence of a 6.5 K magnetic phase transition not arising from the rare earth constituent, but likely associated with the unique isolated ReO3-type Mo8O36 structural subunits in this phase. To better understand the behavior of these materials, electronic structure calculations were performed within density functional theory. Results suggest a magnetic state in which these structural moieties have an internal ferromagnetic arrangement, with small ~1/8 μB moments on each Mo. We suggest that the Mo8O36 units behave like pseudoatoms with spin 1/2 derived from a single hole distributed over the eight Mo atoms that are strongly hybridized with the O atoms of the subunit. Interestingly, while the compound is antiferromagnetic, our calculations suggest that a field-stabilized ferromagnetic state, if achievable, will be a narrow band half-metal.},
doi = {10.1016/j.jssc.2015.03.028},
journal = {Journal of Solid State Chemistry},
number = C,
volume = 227,
place = {United States},
year = {Mon Apr 06 00:00:00 EDT 2015},
month = {Mon Apr 06 00:00:00 EDT 2015}
}
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Works referenced in this record:
Superconductivity of Sodium Tungsten Bronzes
journal, December 1964
- Raub, Ch. J.; Sweedler, A. R.; Jensen, M. A.
- Physical Review Letters, Vol. 13, Issue 25
Superconductivity in hexagonal tungsten bronzes
journal, May 1967
- Remeika, J. P.; Geballe, T. H.; Matthias, B. T.
- Physics Letters A, Vol. 24, Issue 11
Two-dimensional electronic properties of the purple potassium molybdenum bronze K0.9Mo6O17
journal, January 1982
- Buder, R.; Devenyi, J.; Dumas, J.
- Journal de Physique Lettres, Vol. 43, Issue 2
Quasi two-dimensional electronic properties of the lithium molybdenum bronze, Li0.9Mo6O17
journal, September 1984
- Greenblatt, M.; McCarroll, W. H.; Neifeld, R.
- Solid State Communications, Vol. 51, Issue 9
Quasi-two-dimensional electronic properties of the sodium molybdenum bronze, Na0.9Mo6O17
journal, September 1985
- Greenblatt, M.; Ramanujachary, K. V.; McCarroll, W. H.
- Journal of Solid State Chemistry, Vol. 59, Issue 2
Charge Density wave Properties of Molybdenum Bronzes
journal, October 1993
- Dumas, Jean; Schlenker, Claire
- International Journal of Modern Physics B, Vol. 07, Issue 23n24
Sliding charge density waves without damping: Possible fröhlich superconductivity in blue bronze
journal, September 1987
- Mihály, G.; Beauchêne, P.
- Solid State Communications, Vol. 63, Issue 10
Charge-density-wave instabilities in the low-dimensional molybdenum bronzes and oxides
journal, September 1985
- Schlenker, C.; Dumas, J.; Escribe-filippini, C.
- Philosophical Magazine B, Vol. 52, Issue 3
Sliding charge-density wave conductivity in potassium molybdenum bronze
journal, October 1984
- Schneemeyer, L. F.; DiSalvo, F. J.; Fleming, R. M.
- Journal of Solid State Chemistry, Vol. 54, Issue 3
Nonlinerar Transport Phenomena in Molybdenum Oxide Bronzes
journal, April 1985
- Schneemeyer, L. F.; Spengler, S. E.; Disalvo, F. J.
- Molecular Crystals and Liquid Crystals, Vol. 125, Issue 1
Structure and electrical resistivity of the new yellow oxygenated molybdenum bronze GdMo16O44
journal, April 1996
- Galez, Ph.; Moreau, J. -M.; Marcus, J.
- Solid State Communications, Vol. 98, Issue 2
Magnetic properties and 151Eu Mössbauer spectroscopy of a new molybdenum bronze:Eu0.08MoO3
journal, April 1987
- Marcus, J.; Escribe-Filippini, C.; Chevalier, R.
- Solid State Communications, Vol. 62, Issue 4
Magnetic ordering in new rare earth molybdenum bronzes
journal, February 1995
- Escribe Filippini, C.; Marcus, J.
- Journal of Magnetism and Magnetic Materials, Vol. 140-144
CRYSTALS version 12: software for guided crystal structure analysis
journal, November 2003
- Betteridge, Paul W.; Carruthers, J. Robert; Cooper, Richard I.
- Journal of Applied Crystallography, Vol. 36, Issue 6
Generalized Gradient Approximation Made Simple
journal, October 1996
- Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
- Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
Structural anomalies, oxygen ordering and superconductivity in oxygen deficient Ba2YCu3Ox
journal, February 1990
- Cava, R. J.; Hewat, A. W.; Hewat, E. A.
- Physica C: Superconductivity, Vol. 165, Issue 5-6
Preparation of lithium molybdenum oxide bronzes by a temperature gradient flux growth technique
journal, September 1984
- McCarroll, W. H.; Greenblatt, M.
- Journal of Solid State Chemistry, Vol. 54, Issue 2
Crystal growth of alkali metal molybdenum bronzes by a temperature gradient flux technique
journal, December 1984
- Ramanujachary, K. V.; Greenblatt, M.; McCarroll, W. H.
- Journal of Crystal Growth, Vol. 70, Issue 1-2
Fermi surfaces and single-particle spectral functions of low-dimensional inorganic non-cuprate compounds: the molybdenum bronzes
journal, November 1996
- Gweon, G-H; Allen, J. W.; Claessen, R.
- Journal of Physics: Condensed Matter, Vol. 8, Issue 48
Band electronic structure of the molybdenum blue bronze A0.30MoO3 (A = K, Rb)
journal, July 1986
- Whangbo, M. H.; Schneemeyer, L. F.
- Inorganic Chemistry, Vol. 25, Issue 14
The blue bronze K0.3MoO3: A new one-dimensional conductor
journal, February 1981
- Travaglini, G.; Wachter, P.; Marcus, J.
- Solid State Communications, Vol. 37, Issue 7
Synthesis of reduced complex oxides of molybdenum by fused salt electrolysis
journal, July 1983
- McCarroll, William H.; Darling, Cynthia; Jakubicki, Gary
- Journal of Solid State Chemistry, Vol. 48, Issue 2
Redetermination of the structure of LaMo5O8 by single-crystal X-ray diffraction
journal, August 1994
- Gall, P.; Gougeon, P.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 50, Issue 8
Structure of GdMo5O8
journal, February 1991
- Gougeon, P.; Gall, P.; Sergent, M.
- Acta Crystallographica Section C Crystal Structure Communications, Vol. 47, Issue 2
Electronic Structure, Electrical and Magnetic Properties of RMo 8 O 14 Compounds (R = La, Ce, Pr, Nd, Sm) Containing Bicapped Mo 8 Clusters
journal, August 2002
- Gautier, Régis; Andersen, Ole Krogh; Gougeon, Patrick
- Inorganic Chemistry, Vol. 41, Issue 18
The modulated structure of LaMo 8 O 14
journal, June 1993
- Leligny, H.; Labbe, P.; Ledesert, M.
- Acta Crystallographica Section B Structural Science, Vol. 49, Issue 3
Anomalous Metal–Insulator Transitions in Reduced Molybdenum Oxides,A4Mo18O32(A=Ca, Y, Gd–Yb) with Mon(n=2, 4, 6) Cluster Chains
journal, November 1997
- Gall, P.; Gougeon, P.; Ramanujachary, K. V.
- Journal of Solid State Chemistry, Vol. 134, Issue 1
Synthesis, Structural Studies, and Physical Properties of the RE5Mo32O54 (RE=La, Ce, Pr, Nd) Compounds Containing trans-Bicapped Mo8 Octahedral Clusters and Mo7–Mo10–Mo7 Triclusters
journal, July 2000
- Tortelier, J.; Gall, P.; Noël, H.
- Journal of Solid State Chemistry, Vol. 152, Issue 2