First-principles molecular orbital methods and gradient-corrected density functional calculations on silicon clusters are used to study possible pathways for the initial oxidation of Si (100)-2×1. In these reactions, the adsorbed hydroxyl oxygen inserts into the dimer Si–Si bond to form a suboxide (&trpbnd;Si–O–Si&trpbnd;) surface structure. The reaction typically follows a two-step pathway involving an intermediate energy minimum. In the case of an ideal surface with full water coverage, the reaction is exothermic by 1.3 eV and the overall reaction barrier is estimated at 2.4 eV. However, an alternative pathway involving a dangling bond site lowers the activation barrier to 2.1 eV. The implications for the oxidation reaction rates are discussed as well as possible alternative pathways. ©1998 American Institute of Physics.