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Ab initio calculations on the O2 3−-Y3+ center in CaF2 and SrF2: its electronic structure and hyperfine constants

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Abstract

The O2 3−-Y3+ center in fluorite-type structures (CaF2 and SrF2) has been investigated at the density functional theory (DFT) level using the CRYSTAL06 code. Our calculations were performed by means of the hybrid B3PW method in which the Hartree–Fock exchange is mixed with the DFT exchange functional, using Becke’s three parameter method, combined with the non-local correlation functionals by Perdew and Wang. Our calculations confirm the stability and the molecular character of the O2 3−-Y3+ center. The unpaired electron is shown to be almost exclusively localized on and equally distributed between the two oxygen atoms that are separated by a bond distance of 2.47 Å in CaF2 and 2.57 Å in SrF2. The calculated 17O and 19F hyperfine constants for of the O2 3−-Y3+ center are in good agreement with their corresponding experimental values reported by previous electron paramagnetic resonance and electron nuclear double resonance studies, while discrepancies are notable for the 89Y hyperfine constants.

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Acknowledgments

We thank two anonymous reviewers and Dr. M. Matsui for incisive criticism and helpful suggestions, and the Natural Science and Engineering Research Council (NSERC) of Canada for financial support of this study. SMB is also grateful to the University of Saskatchewan for a Dean’s Scholarship. This research has been enabled by the use of WestGrid computing resources, which are funded in part by the Canada Foundation for Innovation, Alberta Innovation and Science, BC Advanced Education, and the participating research institutions. WestGrid equipment is provided by IBM, Hewlett Packard and SGI.

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Authors and Affiliations

  1. Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7K 5E2, Canada

    Sanda M. Botis & Yuanming Pan

  2. Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, UK

    Davy A. Adriaens

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  1. Sanda M. Botis
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  2. Davy A. Adriaens
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Correspondence to Sanda M. Botis.

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Botis, S.M., Adriaens, D.A. & Pan, Y. Ab initio calculations on the O2 3−-Y3+ center in CaF2 and SrF2: its electronic structure and hyperfine constants. Phys Chem Minerals 36, 1–7 (2009). https://doi.org/10.1007/s00269-008-0253-3

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