Abstract
We report studies based on a combination of ab initio electronic structure and Monte Carlo (MC) technique on the problem of cation partitioning among inequivalent octahedral sites, M1 and M2 in mixed olivines containing Mg2+ and Fe2+ ions. Our MC scheme uses interactions derived out of ab initio, density functional calculations carried out on measured crystal structure data. Our results show that there is no reversal of the preference of Fe for M1 over M2 as a function of temperature. Our findings do not agree with the experimental findings of Redfern et al. (Phys Chem Miner 27:630–637, 2000), but are in agreement with those of Heinemann et al. (Eur J Mineral 18:673–689, 2006) and Morozov et al. (Eur J Mineral 17:495–500, 2005).
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Notes
The order–disorder process in olivine is called non-convergent because M1 and M2 sites do not converge to symmetry equivalence even when Fe2+ and Mg2+ become randomly disordered.
Contribution for h vanishes for 50:50 Fe–Mg olivine.
The standard deviations are large for small quantities like J and J′ which are already at the borderline of DFT accuracy.
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We thank funding through Advanced Materials Research Unit.
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Chatterjee, S., Bhattacharyya, S., Sengupta, S. et al. Crossover of cation partitioning in olivines: a combination of ab initio and Monte Carlo study. Phys Chem Minerals 38, 259–265 (2011). https://doi.org/10.1007/s00269-010-0401-4
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DOI: https://doi.org/10.1007/s00269-010-0401-4