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Title: A 2MnXO 4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

Abstract

Four new manganese germanates and silicates, A 2MnGeO 4 (A = Li, Na) and A 2MnSiO 4 (A = Na, Ag), were prepared, and their crystal structures were determined using the X-ray Rietveld method. All of them contain all components in tetrahedral coordination. Li 2MnGeO 4 is orthorhombic (Pmn2 1) layered, isostructural with Li 2CdGeO 4, and the three other compounds are monoclinic (Pn) cristobalite-related frameworks. As in other stuffed cristobalites of various symmetry (Pn A 2MXO 4, Pna2 1 and Pbca AMO 2), average bond angles on bridging oxygens (here, Mn–O–X) increase with increasing A/X and/or A/M radius ratios, indicating the trend to the ideal cubic (Fd$$ \overline{3}\ $$m) structure typified by CsAlO 2. The sublattices of the magnetic Mn 2+ ions in both structure types under study (Pmn2 1 and Pn) are essentially the same; namely, they are pseudocubic eutaxy with 12 nearest neighbors. The magnetic properties of the four new phases plus Li 2MnSiO4 were characterized by carrying out magnetic susceptibility, specific heat, magnetization, and electron spin resonance measurements and also by performing energy-mapping analysis to evaluate their spin exchange constants. Ag 2MnSiO 4 remains paramagnetic down to 2 K, but A 2MnXO 4 (A = Li, Na; X = Si, Ge) undergo a three-dimensional antiferromagnetic ordering. All five phases exhibit short-range AFM ordering correlations, hence showing them to be low-dimensional magnets and a magnetic field induced spin-reorientation transition at T < TN for all AFM phases. We constructed the magnetic phase diagrams for A 2MnXO 4 (A = Li, Na; X = Si, Ge) on the basis of the thermodynamic data in magnetic fields up to 9 T. The magnetic properties of all five phases experimentally determined are well explained by their spin exchange constants evaluated by performing energy-mapping analysis.

Authors:
ORCiD logo [1];  [2];  [1];  [3];  [1]; ORCiD logo [3];  [1];  [4];  [4];  [5];  [4];  [6];  [7]
  1. Chemistry Faculty, Southern Federal University, Rostov-on-Don 344090, Russia
  2. Faculty of Physics, Moscow State University, Moscow 119991, Russia; National Research South Ural State University, Chelyabinsk 454080, Russia
  3. Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, United States
  4. Faculty of Physics, Moscow State University, Moscow 119991, Russia
  5. Kirchhoff Institute for Physics, INF 227, Heidelberg University, D-69120 Heidelberg, Germany
  6. Kirchhoff Institute for Physics, INF 227, Heidelberg University, D-69120 Heidelberg, Germany; Centre for Advanced Materials (CAM), INF 225, Heidelberg University, D-69120 Heidelberg, Germany
  7. Faculty of Physics, Moscow State University, Moscow 119991, Russia; National Research South Ural State University, Chelyabinsk 454080, Russia; National University of Science and Technology “MISiS”, Moscow 119049, Russia
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1480115
DOE Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 56; Journal Issue: 22; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English

Citation Formats

Nalbandyan, Vladimir B., Zvereva, Elena A., Shukaev, Igor L., Gordon, Elijah, Politaev, Vladimir V., Whangbo, Myung-Hwan, Petrenko, Aleksandr A., Denisov, Roman S., Markina, Maria M., Tzschoppe, Michael, Bukhteev, Kirill Yu., Klingeler, Rüdiger, and Vasiliev, Alexander N. A2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties. United States: N. p., 2017. Web. doi:10.1021/acs.inorgchem.7b02130.
Nalbandyan, Vladimir B., Zvereva, Elena A., Shukaev, Igor L., Gordon, Elijah, Politaev, Vladimir V., Whangbo, Myung-Hwan, Petrenko, Aleksandr A., Denisov, Roman S., Markina, Maria M., Tzschoppe, Michael, Bukhteev, Kirill Yu., Klingeler, Rüdiger, & Vasiliev, Alexander N. A2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties. United States. doi:10.1021/acs.inorgchem.7b02130.
Nalbandyan, Vladimir B., Zvereva, Elena A., Shukaev, Igor L., Gordon, Elijah, Politaev, Vladimir V., Whangbo, Myung-Hwan, Petrenko, Aleksandr A., Denisov, Roman S., Markina, Maria M., Tzschoppe, Michael, Bukhteev, Kirill Yu., Klingeler, Rüdiger, and Vasiliev, Alexander N. Tue . "A2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties". United States. doi:10.1021/acs.inorgchem.7b02130.
@article{osti_1480115,
title = {A2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties},
author = {Nalbandyan, Vladimir B. and Zvereva, Elena A. and Shukaev, Igor L. and Gordon, Elijah and Politaev, Vladimir V. and Whangbo, Myung-Hwan and Petrenko, Aleksandr A. and Denisov, Roman S. and Markina, Maria M. and Tzschoppe, Michael and Bukhteev, Kirill Yu. and Klingeler, Rüdiger and Vasiliev, Alexander N.},
abstractNote = {Four new manganese germanates and silicates, A2MnGeO4 (A = Li, Na) and A2MnSiO4 (A = Na, Ag), were prepared, and their crystal structures were determined using the X-ray Rietveld method. All of them contain all components in tetrahedral coordination. Li2MnGeO4 is orthorhombic (Pmn21) layered, isostructural with Li2CdGeO4, and the three other compounds are monoclinic (Pn) cristobalite-related frameworks. As in other stuffed cristobalites of various symmetry (Pn A2MXO4, Pna21 and Pbca AMO2), average bond angles on bridging oxygens (here, Mn–O–X) increase with increasing A/X and/or A/M radius ratios, indicating the trend to the ideal cubic (Fd$ \overline{3}\ $m) structure typified by CsAlO2. The sublattices of the magnetic Mn2+ ions in both structure types under study (Pmn21 and Pn) are essentially the same; namely, they are pseudocubic eutaxy with 12 nearest neighbors. The magnetic properties of the four new phases plus Li2MnSiO4 were characterized by carrying out magnetic susceptibility, specific heat, magnetization, and electron spin resonance measurements and also by performing energy-mapping analysis to evaluate their spin exchange constants. Ag2MnSiO4 remains paramagnetic down to 2 K, but A2MnXO4 (A = Li, Na; X = Si, Ge) undergo a three-dimensional antiferromagnetic ordering. All five phases exhibit short-range AFM ordering correlations, hence showing them to be low-dimensional magnets and a magnetic field induced spin-reorientation transition at T < TN for all AFM phases. We constructed the magnetic phase diagrams for A2MnXO4 (A = Li, Na; X = Si, Ge) on the basis of the thermodynamic data in magnetic fields up to 9 T. The magnetic properties of all five phases experimentally determined are well explained by their spin exchange constants evaluated by performing energy-mapping analysis.},
doi = {10.1021/acs.inorgchem.7b02130},
journal = {Inorganic Chemistry},
issn = {0020-1669},
number = 22,
volume = 56,
place = {United States},
year = {2017},
month = {10}
}