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Single-crystal EPR study of three radiation-induced defects (Al–O2 3−, Ti3+ and W5+) in stishovite

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Abstract

Single-crystal electron paramagnetic resonance spectra of electron-irradiated stishovite, measured at temperatures from 3.5 to 294 K, reveal three S = 1/2 radiation-induced defects: an aluminum-associated oxygen hole center and two nd 1 centers (Ti3+ and W5+). The aluminum-associated oxygen hole center, characterized by an orthorhombic site symmetry, coaxial matrices of the electronic Zeeman g, nuclear hyperfine A(27Al) and nuclear quadrupole P(27Al), and the orientation of the g-minimum axis along an O–O direction and those of the unique A(27Al) and P(27Al) axes perpendicular to the O–O direction, is an Al–O2 3− center, with the unpaired electron equally distributed on two equatorial oxygen atoms of a substitutional Al3+ ion at the octahedral Si site. Fully optimized Al-doped structure, theoretical 27Al nuclear hyperfine and quadrupole coupling constants and directions, and 3D spin densities from periodic hybrid density functional theory calculations provide further support for this structural model. Spin Hamiltonian parameters of the Ti3+ and W5+ centers, which are confirmed by their diagnostic 47Ti, 49Ti and 183W hyperfine structures, arise from electron trapping on substitutional Ti4+ and W6+ ions at the octahedral Si site.

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Acknowledgments

We wish to thank Dr. M. Matsui and two anonymous reviewers for constructive comments and helpful suggestions, NSERC for financial support of this study and Ms. Jinru Lin for preparation of Fig. 1. All DFT calculations have been made by the use of Westgrid computing resources, which are funded in part by the Canadian 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, S7N 5E2, Canada

    Yuanming Pan, Mao Mao, Zucheng Li & Sanda M. Botis

  2. VS Sobolev Institute of Geology and Mineralogy Petrology, Siberian Branch of Russian Academy of Sciences, Novosibirsk, 630090, Russia

    Rudolf I. Mashkovtsev & Anton Shatskiy

  3. Department of Earth and Planetary Material Science, Graduate School of Science, Tohoku University, Sendai, 980-8578, Japan

    Anton Shatskiy

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  1. Yuanming Pan
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  2. Mao Mao
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Correspondence to Yuanming Pan.

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Pan, Y., Mao, M., Li, Z. et al. Single-crystal EPR study of three radiation-induced defects (Al–O2 3−, Ti3+ and W5+) in stishovite. Phys Chem Minerals 39, 627–637 (2012). https://doi.org/10.1007/s00269-012-0517-9

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