One advantage of calculating the NMR spectrum from first principles, is that the calculations retain an individual spectrum for each atom in the model. In this way, we can construct spectra based on atom-specific coordination environments. Using a crystal-symmetry metric (CSM) , a measure of the relative distortion from perfect symmetry was extracted for each site in the model. A comparison of the CSM to isotropic chemical shift (Fig. ), shows that the majority of tetrahedral sites are distorted (CSM > 4) , which agrees with the wide quadrupolar distribution of Al(IV) shifts in experimental MQMAS. Separating the spectra into the closest geometric environment, as shown in Fig. , determines that within the a-Al2O3, there exist two types of Al(V) environments, square pyramidal and trigonal bipyramidal; these sites combine to make the Al(V) peak in the 1D NMR at 40 ppm, with a range of site-specific shifts from 20 to 60 ppm. Given Al(V)s unique appearance in amorphous Al2O3 phases, this identification of two geometries of Al(V) sites suggests that further work should involve identifying the role of each geometry in electronic devices. The first principles model of a-Al2O3 enables the construction of these two sites' spectra, where experimental NMR shows them as overlapping.