Abstract
We report on the magneto-structural properties of the rare copper aluminum hydroxo-arsenate mineral liroconite with chemical composition Cu2AlAs1−x P x O4(OH)4·4H2O (x ≈ 0.2). In order to characterize the natural mineral sample chemical analyses, X-ray single crystal and powder diffraction, heat capacity and crystal water desorption, anisotropic thermal expansion and Raman scattering and magnetic susceptibility investigations have been carried out. The magnetic properties are well described by two discrete oxygen bridged Cu2+ spin S = 1/2 dimers with antiferromagnetic spin exchange ranging between −320 K and −136 K, depending on to which group-15 five-valent cation, As5+ or P5+, the dimer bridging oxygen atoms coordinate to. Accordingly the temperature dependence of the magnetic susceptibilities can be well fitted to a sum of two Bleaney–Bowers type spin S = 1/2 dimer susceptibilities suggesting that the dimers show negligible mixed coordination to (AsO4)3−/(PO4)3− tetrahedra. DFT + U calculation confirm the ratio of the spin exchange parameters of the (AsO4)3− or (PO4)3− coordinated Cu2+ – Cu2+ dimers. Inter dimer spin exchange is about two orders of magnitude smaller than intra dimer exchange.
Acknowledgments
We thank V. Duppel for the careful photographical work and the microprobe EDX analyses.
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Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
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Research funding: None declared.
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Conflict of interest statement: The authors declare no conflicts of interest regarding this article.
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