Abstract
Internal surfaces of nanocavities are an exceptionally useful laboratory wherein one can spotlight the factors ruling the intricate interplay between morphology and chemistry at silicon surfaces. At the same time, they offer unparalleled opportunities to validate the assignment of vibrational signals of silicon-terminating species under almost ideal experimental conditions. In the case of hydrogen, evidence will be provided of the detailed evolution of H-related species at surfaces depending on their orientation. Also, preliminary results concerning nitrogen at and around nanocavity surfaces will be reported.