NMR is a method available for validating the local atomic structure while XAS is a measurement for probing the local electronic structure of a-Al2O3. The Al K-edge XAS spectrum shown in Fig. , exhibits three main features; a pre-edge feature (a) and two dominant broad peaks at 1565 eV (b) and 1570 eV (c) which are similar to those in Al-rich glasses and attributed to transitions in Al(IV) and Al(VI) respectively. The absorption edge for Al(V) lies between Al(IV) and Al(VI), and has no experimental reference. Calculating core-hole spectra for all Al sites in the amorphous model, determines the location of this Al(V) absorption edge between 1565 and 1570 eV (Fig. ), and confirms the absorption energy of the Al(IV) and Al(VI) peaks, implying that the model's electronic structure is consistent with the experimental a-Al2O3. Left panel is experimental spectra, the right panel is calculated spectra with quadrupolar effects calculated using SIMPSON . Two lower field spectra were measured using a one pulse sequence, and the high field spectrum was measured using a Hahn-echo pulse sequence. Spinning sidebands are marked with asterisks in the experimental spectra. Experimental fitting was obtained using a Czejek model. DFT-calculated spectra show Al(V) lineshapes separated into square pyramidal and trigonal bipyramidal environments. These calculated spectra represent the first known DFT-calculated NMR lineshapes of amorphous materials and show excellent comparison to the experimental spectra. At higher fields in both cases the three peaks (Al(IV,V,VI)) become more pronounced, and are easily identifiable as separate environments.