Correlated proton disorder in the crystal structure of the double hydroxide perovskite CuSn(OH)$_6$

Fuente: arXiv
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Autores principales: Kulbakov, Anton A., Häußler, Ellen, Parui, Kaushick K., Chakkingal, Aswathi Mannathanath, Pavlovskii, Nikolai S., Pomjakushin, Vladimir Yu., Cañadillas-Delgado, Laura, Hansen, Thomas, Peets, Darren C., Doert, Thomas, Inosov, Dmytro S.
Formato: Preprint
Publicado: 2024
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author Kulbakov, Anton A.
Häußler, Ellen
Parui, Kaushick K.
Chakkingal, Aswathi Mannathanath
Pavlovskii, Nikolai S.
Pomjakushin, Vladimir Yu.
Cañadillas-Delgado, Laura
Hansen, Thomas
Peets, Darren C.
Doert, Thomas
Inosov, Dmytro S.
author_facet Kulbakov, Anton A.
Häußler, Ellen
Parui, Kaushick K.
Chakkingal, Aswathi Mannathanath
Pavlovskii, Nikolai S.
Pomjakushin, Vladimir Yu.
Cañadillas-Delgado, Laura
Hansen, Thomas
Peets, Darren C.
Doert, Thomas
Inosov, Dmytro S.
contents CuSn(OH)$_6$ is a quantum spin system from the family of magnetic double perovskite hydroxides, having a frustrated magnetic sublattice. It is also known as the natural mineral mushistonite, whose crystal structure has remained elusive for decades. Here we employ x-ray and neutron powder diffraction to solve the crystal structure of CuSn(OH)$_6$ and propose a structure model in the orthorhombic space group $Pnnn$ with correlated proton disorder. The occupation of the hydrogen sites in the structure is constrained by ``ice rules'' similar to those known for water ice. The resulting frustration of the hydrogen bonding network is likely to have a complex and interesting interplay with the strong magnetic frustration expected in the face-centred magnetic sublattice. Structural distortions, which are quite pronounced in Cu$^{2+}$ compounds due to the Jahn-Teller effect, partially alleviate both types of frustration. We also show that hydrostatic pressure tends to suppress proton disorder through a sequence of proton-ordering transitions, as some of the split hydrogen sites merge already at 1.75 GPa while others show a tendency toward possible merging at higher pressures.
format Preprint
id arxiv_https___arxiv_org_abs_2410_13359
institution arXiv
publishDate 2024
record_format arxiv
spellingShingle Correlated proton disorder in the crystal structure of the double hydroxide perovskite CuSn(OH)$_6$
Kulbakov, Anton A.
Häußler, Ellen
Parui, Kaushick K.
Chakkingal, Aswathi Mannathanath
Pavlovskii, Nikolai S.
Pomjakushin, Vladimir Yu.
Cañadillas-Delgado, Laura
Hansen, Thomas
Peets, Darren C.
Doert, Thomas
Inosov, Dmytro S.
Materials Science
CuSn(OH)$_6$ is a quantum spin system from the family of magnetic double perovskite hydroxides, having a frustrated magnetic sublattice. It is also known as the natural mineral mushistonite, whose crystal structure has remained elusive for decades. Here we employ x-ray and neutron powder diffraction to solve the crystal structure of CuSn(OH)$_6$ and propose a structure model in the orthorhombic space group $Pnnn$ with correlated proton disorder. The occupation of the hydrogen sites in the structure is constrained by ``ice rules'' similar to those known for water ice. The resulting frustration of the hydrogen bonding network is likely to have a complex and interesting interplay with the strong magnetic frustration expected in the face-centred magnetic sublattice. Structural distortions, which are quite pronounced in Cu$^{2+}$ compounds due to the Jahn-Teller effect, partially alleviate both types of frustration. We also show that hydrostatic pressure tends to suppress proton disorder through a sequence of proton-ordering transitions, as some of the split hydrogen sites merge already at 1.75 GPa while others show a tendency toward possible merging at higher pressures.
title Correlated proton disorder in the crystal structure of the double hydroxide perovskite CuSn(OH)$_6$
topic Materials Science
url https://arxiv.org/abs/2410.13359