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Single-crystal EPR and DFT study of a VIAl–O−–VIAl center in jeremejevite: electronic structure and 27Al hyperfine constants

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Abstract

Single-crystal electron paramagnetic resonance (EPR) spectra of a gem-quality jeremejevite, Al6B5O15(F, OH)3, from Cape Cross, Namibia, reveal an S = 1/2 hole center characterized by an 27Al hyperfine structure arising from interaction with two equivalent Al nuclei. Spin-Hamiltonian parameters obtained from single-crystal EPR spectra at 295 K are as follows: g 1 = 2.02899(1), g 2 = 2.02011(2), g 3 = 2.00595(1); A 1/g e β e  = −0.881(1) mT, A 2/g e β e  = −0.951(1) mT, and A 3/g e β e  = −0.972(2) mT, with the orientations of the g 3- and A 3-axes almost coaxial and perpendicular to the Al–O–Al plane; and those of the g 1- and A 1-axes approximately along the Al–Al and Al–OH directions, respectively. These results suggest that this aluminum-associated hole center represents hole trapping on a hydroxyl oxygen atom linked to two equivalent octahedral Al3+ ions, after the removal of the proton (i.e., a VIAl–O−–VIAl center). Periodic ab initio UHF and DFT calculations confirmed the experimental 27Al hyperfine coupling constants and directions, supporting the proposed structural model. The VIAl–O−–VIAl center in jeremejevite undergoes the onset of thermal decay at 300 °C and is completely bleached at 525 °C. These data obtained from the VIAl–O−–VIAl center in jeremejevite provide new insights into analogous centers that have been documented in several other minerals.

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Acknowledgments

We thank Dr. Milan Rieder and two reviewers for incisive criticisms and helpful suggestions and Natural Science and Engineering Research Council (NSERC) of Canada for financial support. DFT calculations in this research have been enabled 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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  1. Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK, S7N 5E2, Canada

    Rong Li, Zucheng Li & Yuanming Pan

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  1. Rong Li
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Correspondence to Yuanming Pan.

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Li, R., Li, Z. & Pan, Y. Single-crystal EPR and DFT study of a VIAl–O−–VIAl center in jeremejevite: electronic structure and 27Al hyperfine constants. Phys Chem Minerals 39, 491–501 (2012). https://doi.org/10.1007/s00269-012-0505-0

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