We investigate the dielectric permittivity of SiO2 on Si(100) substrates using a first-principles approach. It is shown that both the static and high-frequency dielectric constants of the oxide overlayer increase when the oxide thickness is reduced. This behavior of the overlayer is found to be well reproduced by a classical two-layer model in which the pure oxide and the suboxide layer are treated as distinct dielectrics. Implications for interfaces between silicon and high-k gate oxides are discussed. (C) 2004 Elsevier B.V. All rights reserved.