We have re-investigated the well-studied hydrogen covered Si(100) surface using high resolution electron energy loss spectroscopy (HREELS) with a spectral resolution down to 13 cm1, representing an improvement by a factor of 3–4 compared to earlier work. For the first time in HREELS, it has been possible to clearly distinguish between the stretching vibrations of H-Si-Si-H units on monohydride surfaces with a 2×1 low energy electron diffraction pattern, on the one hand, and SiH2 units on dihydride surfaces with 1×1 symmetry on the other hand, the two being shifted by 5 cm-1 with respect to each other, in good agreement with results from infrared spectroscopy. Furthermore, we find trihydride units even for relatively low exposures beyond monohydride saturation coverage from their distinct stretching frequencies, and this points towards early etching stages. The question of the scattering mechanism applicable in our experiments is discussed. Since there are no spectral limitations in HREELS, we can analyze the bending and scissor vibrations with similar accuracy as the stretching vibration. Again, we observe fine structure in our loss peaks, the umbrella mode, for example, giving once more evidence for trihydride species at the surface. The complicated line shape of all vibrational modes can thus be used to deduce detailed structural information about the surface atomic structure, opening up entirely new possibilities by employing HREELS for the structural characterization of (silicon) surfaces with atomic hydrogen as a local probe. © 1998 American Institute of Physics.