The nature of the elusive muonium centre in sulphur is re-examined in the light of new data on its level-crossing resonance and spin–lattice relaxation. The aim is to provide a model for the solid-state chemistry of interstitial hydrogen in this element, which is as yet unknown, as well as to solve one of the longest standing puzzles in μSR spectroscopy, namely the surprisingly strong depolarization of muons mimicking ion-implanted protons in this innocuous non-magnetic material. The paramagnetic muonium (and by inference hydrogen) centre is confirmed to have the character of a molecular radical, but with huge anisotropy at cryogenic temperatures and a striking shift of the resonance at ordinary temperatures, the hyperfine parameters appearing to collapse and vanish towards the melting point. New density-functional supercell calculations identify a number of possible structures for the defect centre, including a novel form of bond-centred muonium in a closed-ring S8Mu complex. Simulations of the spin dynamics and fits to the spectra suggest a dynamical equilibrium or chemical exchange between several configurations, with occupancy of the bond-centre site falling from unity at low cryogenic temperatures to zero near the melting point.
