This article applies x-ray absorption spectroscopy to a study of the electronic structure of the high-k gate dielectrics, TiO2, ZrO2, and HfO2. Qualitative and quantitative differences are identified between intra-atomic transitions such as the Zr 3 p-state, M-2,M-3 core state absorptions which terminate in TM 4d*- and 5s*-states, and inter-atomic transitions such as the Zr 1 s- and O 1 s-state K, absorptions which terminate in Zr 4d*- and 5s*-states that are mixed with O atom 2p* states through nearest neighbor bonding interactions. Differences between the spectral peak energies of the lowest d*-features in the O K I spectra are demonstrated to scale with optical band gap differences for TiO2, ZrO2, and HfO2, providing important information relevant to applications of TM oxides as high-K gate dielectrics in advanced Si devices. This is demonstrated through additional scaling relationships between (i) conduction band offset energies between Si and the respective dielectrics, and the optical band gaps, and (ii) the conduction band offset energies, and the electron tunneling masses as well. (C) 2004 American Vacuum Society.