Reaction mechanisms for oxidation of the Si(100) surface by atomic oxygen were studied with high-level quantum mechanical methods in combination with a hybrid QM/MM (Quantum mechanics/Molecular Mechanics) method. Consistent with previous experimental and theoretical results, three structures, “back-bond”, “on-dimer”, and “dimer-bridge”, are found to be the most stable initial surface products for O adsorption (and in the formation of SiO2 films, i.e., passive oxidation). All of these structures have significant diradical character. In particular, the “dimer-bridge” is a singlet diradical. Although the ground state of the separated reactants, O+Si(100), is a triplet, once the O atom makes a chemical bond with the surface, the singlet potential energy surface is the ground state. With mild activation energy, these three surface products can be interconverted, illustrating the possibility of the thermal redistribution among the initial surface products. Two channels for SiO desorption (leading to etching, i.e., active oxidation) have been found, both of which start from the back-bond structure. These are referred to as the silicon-first (SF) and oxygen-first (OF) mechanisms. Both mechanisms require an 89.8 kcal/mol desorption barrier, in good agreement with the experimental estimates of 80−90 kcal/mol. “Secondary etching” channels occurring after initial etching may account for other lower experimental desorption barriers. The calculated 52.2 kcal/mol desorption barrier for one such secondary etching channel suggests that the great variation in reported experimental barriers for active oxidation may be due to these different active oxidation channels.