Structural principles of cation ordering and octahedral tilting in A-site ordered double perovskites: ferroelectric CaMnTi2O6 as a model system

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A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä

Date

2022-11-21

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en

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9

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Dalton Transactions, Volume 51, issue 43, pp. 16508-16516

Abstract

We have used quantum chemical methods to study the structural principles and energetics of A-site ordered AA'B2O6 double perovskites. 33 combinations of A-site ordering and Glazer tilting have been systematically studied for the ferroelectric CaMnTi2O6 model system. The used approach was able to predict the correct combination of A-site ordering and tilting of octahedra in comparison to the experimentally known CaMnTi2O6. The energy differences between the various combinations of A-site ordering and tilt systems show a large variation of tens of kJ mol-1 per formula unit, which suggests that the methodology used here can be used as a starting point for making reliable predictions on the structures of yet unknown A-site ordered double perovskites. The energy differences due to A-site ordering and octahedral tilting were larger compared to the energy difference arising from ferroelectric distortion in CaMnTi2O6. The energy differences between various hypothetical double perovskite structures could be explained by studying their structural characteristics in detail. The relative energies are closely correlated with the Mn-O distances and Mn coordination in the studied structures.

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We thank the Academy of Finland for funding (Grant No. 317273) and CSC – The Finnish IT Center for Science for computational resources.

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GROUP-THEORETICAL ANALYSIS, CRYSTAL, DISTORTIONS, DESIGN

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Citation

Albrecht, E K & Karttunen, A J 2022, ' Structural principles of cation ordering and octahedral tilting in A-site ordered double perovskites: ferroelectric CaMnTi 2 O 6 as a model system ', Dalton Transactions, vol. 51, no. 43, pp. 16508-16516 . https://doi.org/10.1039/d2dt02283d