Single-crystal EPR study of three radiation-induced defects (Al–O23?/sup>, Ti3+ and W5+) in stishovite

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• 作者：Yuanming Pan (1) yuanming.pan@usask.ca
  Mao Mao (1)
  Zucheng Li (1)
  Sanda M. Botis (1)
  Rudolf I. Mashkovtsev (2)
  Anton Shatskiy (23)
• 关键词：Stishovite – Radiation ; induced defects – Al–O2 3? – Ti3+ – W5+ – Single ; crystal EPR – Hyperfine structures – DFT calculations – Rutile ; type oxides
• 刊名：Physics and Chemistry of Minerals
• 出版年：2012
• 出版时间：September 2012
• 年：2012
• 卷：39
• 期：8
• 页码：627-637
• 全文大小：529.1 KB
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• 作者单位：1. Department of Geological Sciences, University of Saskatchewan, Saskatoon, SK S7N 5E2, Canada2. VS Sobolev Institute of Geology and Mineralogy Petrology, Siberian Branch of Russian Academy of Sciences, Novosibirsk, 630090 Russia3. Department of Earth and Planetary Material Science, Graduate School of Science, Tohoku University, Sendai, 980-8578 Japan
• ISSN：1432-2021

文摘

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.