We have recently observed spectrally resolved vibronic structure and luminescence intermittency from nanometer-size porous silicon nanocrystals. In this study we examine the quantum efficiency of a single nanoparticle and show that emitting nanoparticles do so with near unity quantum efficiency. This result suggests that the emission from porous Si nanoparticles, and thus bulk porous Si, results from a small number of high quantum efficiency emitters. In our previous work we have shown that our nanoparticles contain more than one coupled chromophore. In order to examine these effects more closely we employ several spectroscopy and microscopy techniques including: 1) single-particle spectroscopy, 2) shear-force microscopy, and 3) time-resolved spectroscopy, on a colloidal suspension of size-selected, surface-oxidized nanoparticles. In addition we apply statistical techniques to provide a more complete picture of the coupling between chromophores in a given nanoparticle.