Abstract
Optical absorption spectra of siderite were taken across the high-spin (HS)-to-low-spin (LS) transition up to a pressure of 70 GPa in the spectral range between 28,500 and 10,000 cm−1. Up to a pressure of 44.5 GPa, a pair of two overlapping broad bands was observed that are caused by the electronic spin-allowed 5 T 2g → 5 E g transition of the octahedrally coordinated Fe2+. Furthermore, eight spin-forbidden bands are observable at high pressures up to 44.5 GPa, but they are gradually overlapped by the increasing high-energy absorption edge to be tracked down over the whole pressure range. Due to the HS-to-LS-spin-state transition of Fe2+ between 44.5 and 47.6 GPa, a new broad intense absorption band appears on the steep background of the edge, which is assigned to the electronic spin-allowed 1 A 1g → 1 T 1g transition of octahedral Fe2+ in LS configuration. We estimated a mean octahedral module \(\text{K}_{\text{oct}}^{\text{spectr}}\) of Fe2+ in the LS state for pressure range 47.6–65.5 GPa as 263 (17) GPa. Especially, a strong intensification of the spin-allowed and spin-forbidden bands with increasing pressure is observed in the HS state. This is assumed to be caused by the borrowing of intensity from the UV absorption bands, which are allowed by the Laporte selection rule and are caused by electronic ligand-to-metal charge-transfer transitions.
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Notes
Aside HS–LS transitions, in the literature, this phenomenon is also called spin-pairing transition, spin crossover, spin collapse, and magnetic collapse.
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Acknowledgements
We thank Larisa Solomatina (Kiev) for providing us with the sample of natural siderite and its microprobe analyses. We are also thankful to Michal Stekiel, Chris Fruhner, Lkhamsuren Bayarjargal, and Björn Winkler (Frankfurt) for discussion and their help with the preparation and the loading of the Boehler–Almax DAC. We further thank Barbara Lavina, Las Vegas, USA for her help in this study. We are also thankful to two anonymous reviewers for constructive critics and reasonable remarks and suggestions which significantly improved the paper. This work is part of the DFG funded research group FOR2125 CarboPaT (Ko1260/16, JA1469/9).
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Taran, M.N., Müller, J., Friedrich, A. et al. High-pressure optical spectroscopy study of natural siderite. Phys Chem Minerals 44, 537–546 (2017). https://doi.org/10.1007/s00269-017-0880-7
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DOI: https://doi.org/10.1007/s00269-017-0880-7