After x-ray irradiation at 20 K, an intrinsic O- centre was
identified by ESR and ENDOR spectroscopy as the self-trapped hole
centre in ZnWO4. Observation of one Zn and two strong W
superhyperfine interactions allows us to distinguish between two
possible trapping sites: the hole resides at the B-type oxygen
position which has one Zn and two W nearest neighbours. Broadening
of the ESR lines and averaging of the g-value is observed and
explained as due to thermally activated hopping of the hole between
two energetically equivalent oxygen positions. The activation
energy of this reorientation is found to be 0.016±0.003 eV. The
thermal decay of the intrinsic O- centre, and its connection to
thermoluminescence, has been studied; it shows that this centre
cannot be the luminescence centre for the typical TL emission at
~480 nm in ZnWO4. This emission may be due to an
intrinsic electron-type defect.