The structural characterization, electronic spectroscopy, and excited-state dynamics of surface-oxidized Si nanocrystals, prepared in a high-temperature aerosol apparatus, are studied to gain insight into the emission mechanism of visible light from these systems. The results are compared with direct-gap CdSe nanocrystals, indirect-gap AgBr nanocrystals, bulk crystalline silicon, and porous silicon thin films. As the size of the Si crystallites decreases to 1-2 nm in diameter, the band gap and luminescence energy correspondingly increase to near 2.0 eV, or 0.9 eV above the bulk 1.1-eV band gap. The absorption and luminescence spectra remain indirect-gap-like with strong transverse optical vibronic origins. The quantum yield increases to about 5% at room temperature, but the unimolecular radiative rate remains quite long, similar to 10(-3)-10(-4) s(-1) The luminescence properties of Si nanocrystals and porous Si are consistent, in most respects, with simple emission from size-dependent, volume-quantum-confined nanocrystal states. Room-temperature quantum yields increase not because coupling to the radiation field is stronger in confined systems, but because radiationless processes, which dominate bulk Si emission, are significantly weaker in nanocrystalline Si. An analogous series of changes occurs in nanocrystalline AgBr. While previous work on CdSe and CuCl nanocrystals has revealed size regimes for their spectroscopic properties, the Si and AgBr nanocrystal studies are shown here to reveal additional size regimes for their kinetic properties.