Performance and reliability in semiconductor devices are limited by electronically active defects, primarily O-atom and N-atom vacancies. Synchrotron X-ray spectroscopy results, interpreted in the context of two-electron multiplet theories, have been used to analyze conduction band edge, and O-vacancy defect states in nano-crystalline transition metal oxides, e.g., HfO2, and the noncrystalline dielectrics, SiO2, Si3N4 and Si-oxynitride alloys. Two-electron multiplet theory been used to develop a high-spin state equivalent d2 model for O-vacancy allowed transitions and negative ion states as detected by X-ray absorption spectroscopy in the O K pre-edge regime. Comparisons between theory and experiment have used Tanabe-Sugano energy level diagrams for determining the symmetries and relative energies of intra-d-state transitions for an equivalent d2 ground state occupancy. Trap-assisted-tunneling, Poole-Frenkel hopping transport, and the negative bias temperature instability have been explained in terms of injection and/or trapping into O-atom and N-atom vacancy sites, and applied to gate dielectric, and metal-insulator-metal structures.