A 2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

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.

doi:10.1021/acs.inorgchem.7b02130

Title: A ₂MnXO₄ Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

Journal Article · Tue Oct 31 00:00:00 EDT 2017 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.7b02130· OSTI ID:1480115

^[1]; Zvereva, Elena A. ^[2]; Shukaev, Igor L. ^[1]; Gordon, Elijah ^[3]; Politaev, Vladimir V. ^[1];

^[3]; Petrenko, Aleksandr A. ^[1]; Denisov, Roman S. ^[4]; Markina, Maria M. ^[4]; Tzschoppe, Michael ^[5]; Bukhteev, Kirill Yu. ^[4]; Klingeler, Rüdiger ^[5]; Vasiliev, Alexander N. ^[6]

Southern Federal Univ. (Russia)
Moscow State Univ., Moscow (Russian Federation); National Research South Ural State Univ., Chelyabinsk (Russia)
North Carolina State Univ., Raleigh, NC (United States)
Moscow State Univ., Moscow (Russian Federation)
Heidelberg Univ. (Germany)
Moscow State Univ., Moscow (Russian Federation); National Research South Ural State Univ., Chelyabinsk (Russia); National Univ. of Science and Technology (MISiS), Moscow (Russia)

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.

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Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1480115

Journal Information:: Inorganic Chemistry, Vol. 56, Issue 22; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 16 works

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Title: A 2MnXO4 Family (A = Li, Na, Ag; X = Si, Ge): Structural and Magnetic Properties

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