The anomalous, low-stress, shock initiation of detonation observed in earlier studies of pentaerythritol tetranitrate single crystals was examined in more detail experimentally. Time-resolved particle-velocity histories were obtained for [110], [001] and [100] orientations of single-crystal pentaerythritol tetranitrate explosive for shock input stresses of 4–7 GPa using laser interferometry instrumentation. At about 4.2 GPa an elastic-plastic, two-wave structure was noted in [110] and [001] orientations, and a single shock wave for [100] orientation. The two-wave structure provides an explanation for the anomalous shock initiation sensitivity and intermediate velocity transition previously observed in [110] orientation at this stress level. It also explains details of fluorescent emission histories from [110] and [001] crystals previously measured. The orientation-dependent results are consistent with the model of steric hindrance to shear at the molecular level. Fits to the elastic Hugoniot data in [110] and [001] orientations are given as well as a revised fit for the bulk Hugoniot. ©1997 American Institute of Physics.