An all-electron study of the low-lying excited states and optical constants of Al 2 O 3 in the range 5-80 eV

This paper reports calculated energies and electronic structures of O(2p), O(2s) and Al(2p) excited states in bulk α-Al2O3, at the {0001} and {1010} surfaces and in the presence of O vacancy defects, obtained from all-electron HF, B3LYP, GGA and LDA calculations based on a recently described direct Δ-SCF approach.1 The closely related frequency-dependent optical constants derived from B3LYP calculations within the CPHF/DF framework are also reported, where both sets of results are shown to compare favourably with the experimental spectra. The differences between the directly calculated excited state energies, which in α-Al2O3 are equal to the leading excitation edges, based on the four functionals, are substantially less than the differences between the corresponding (ground state) band gaps, as reported previously for AFII NiO.1 For the B3LYP functional, these energies are 8.7 eV, 12.5 eV and 73.7 eV for the O(2p), O(2s) and Al(2p) excitations respectively. The O(2p) edge is predicted to be degenerate, with distinct excitations from O(2p) states that are parallel to and perpendicular to the c-axis, in agreement with reported spectra.2 The calculations reported suggest a modified interpretation of the uv spectrum to that previously suggested.3 Detailed analyses of the charge and spin distributions in the four bulk excited states indicate that these are essentially charge-transfer excitonic, with acceptor sites at the nearest neighbour positions. Despite the close proximity of the O(2p||) and O(2p⊥) excited state energies, the charge and spin distributions are predicted to be quite different.