Radiation-induced defects in quartz. III. Single-crystal EPR,ENDOR and ESEEM study of a peroxy radical

The X- and W-band single-crystal electron paramagnetic resonance spectra of an electron-irradiated natural quartz permit quantitative analysis of a ²⁹Si hyperfine structure (A ~12.6 MHz) and an ²⁷Al hyperfine structure (A ≤ 0.8 MHz) for a previously reported hole-like center. The ²⁹Si hyperfine structure arises from interaction with two equivalent Si atoms and is characterized by the direction of the unique A axis close to a Si–O bond direction. The ²⁷Al hyperfine structure, confirmed by pulsed electron nuclear double resonance and electron spin echo envelope modulation spectra, is characterized by the unique A axis approximately along a twofold symmetry axis. These ²⁹Si and ²⁷Al hyperfine data, together with published theoretical results on peroxy radicals in SiO₂ as well as our own density functional theory (DFT) calculations on model peroxy centers, suggest this hole-like center to have the unpaired spin on a pair of oxygen atoms linked to two symmetrically equivalent Si atoms and a substitutional Al³⁺ ion across the c-axis channel, a first peroxy radical in quartz. The nuclear quadrupole matrix P also suggests that the Al³⁺ ion corresponds closely to the diamagnetic precursor to the [AlO₄]⁰ center. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.