An all-electron study of the low-lying excited states and optical constants of Al₂O₃ in the range 5-80 eV

William Mackrodt (1) , Michel Rérat (2) , Francesco Silvio Gentile (3) , Roberto Dovesi (4)

1 Dipartimento di Chimica [Torino]
2 IPREM - Institut des sciences analytiques et de physico-chimie pour l'environnement et les materiaux
3 Dipartimento di chimica (IFM)
4 Dipartimento di Chimica and Centre of Excellence NIS

97 Total downloads 1 1 citation on Dimensions. Turn on MathJax Get permission to re-use this article Share this article Share this content via email Share on Facebook Share on Twitter Share on Google+ Share on Mendeley Article information Abstract This paper reports calculated energies and electronic structures of O(2p), O(2s) and Al(2p) excited states in bulk -Al2O3, at the and 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 -SCF approach (Mackrodt et al 2018 J. Phys.: Condens. Matter 30 495901). 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 -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 (Mackrodt et al 2018 J. Phys.: Condens. Matter 30 495901). 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 the reported spectra (Tomiki et al 1993 J. Phys. Soc. Japan 62 573). 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() and O(2p) excited state energies, the charge and spin distributions are predicted to be quite different.

Domaines: Chimie; Chimie théorique et/ou physique

William Mackrodt, Michel Rérat, Francesco Silvio Gentile, Roberto Dovesi. An all-electron study of the low-lying excited states and optical constants of Al₂O₃ in the range 5-80 eV. Journal of Physics: Condensed Matter, 2019, 32 (8), pp.085901. ⟨10.1088/1361-648X/ab4c0e⟩. ⟨hal-02310131⟩