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The atomic arrangement and electronic interactions in vonsenite at 295, 100, and 90 K

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Published/Copyright: December 28, 2021
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Abstract

Vonsenite, Fe22+Fe3+O2BO3, has been the subject of many studies in the materials science and condensed matter physics communities due to interest in the electronic and magnetic properties and ordering behavior of the phase. One such study, undertaken on synthetic material of end-member composition, reports X‑ray diffraction structure refinements that indicate a phase transition from Pbam to Pbnm at or just below ~283 K, determined subsequently to arise from a Peierls-like instability. To compare the stability of the natural phase with that of synthetic material, we performed high-precision X‑ray crystal-structure analyses at 295, 100, and 90 K (R1 = 0.0119, 0.0186, and 0.0183, respectively), Mössbauer spectroscopy at 295, 220, 150, 80, and 4.2 K, and wavelength-dispersive electron microprobe analysis on a vonsenite of near-end-member composition from Jayville, New York, U.S.A. The Pbnm structure is observed at 100 and 90 K, suggesting similar phase stability for the natural and synthetic phases. Comparison of Mössbauer data and X‑ray site occupancies between the natural and synthetic phases suggests a reinterpretation of Mössbauer site assignments. We conclude that the Peierls-like instability underlying the reported transition from Pbam to Pbnm in synthetic material also occurs in our specimen of natural near-end-member vonsenite at temperatures between 295 and 100 K.

Acknowledgments and Funding

Edward Bonner worked on early structure refinements of vonsenite. M.M. expresses deep gratitude for the privilege of having been a student of Charles T. Prewitt and the late Roger G. Burns. Consummate experimentalists, visionary thinkers, mentors at once thoughtful and demanding, Charlie and Roger are lions of mineralogy, central to the evolution and transformation of the discipline from its descriptive origins to a quantitative science with a nascent capacity for prediction: from what, to how and why. The manuscript was improved by reviews by two anonymous reviewers and a Technical Reviewer, and expertly handled by Associate Editor Aaron Lussier, for which we are very appreciative; thanks are also due to the American Mineralogist Technical Editor team for a discussion of detection of the superstructure in an early manuscript version. Support for this work was provided by the National Science Foundation through Grant NSF-MRI 1039436 to J.M.H.

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Received: 2020-10-12
Accepted: 2021-01-21
Published Online: 2021-12-28
Published in Print: 2022-01-27

© 2022 Mineralogical Society of America

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