To test the latter hypothesis, ωB97X-D/def2-SVP geometry optimizations were performed to verify the GFN2 optimized geometries. Five molecules containing torsion pattern 270 and an angle of ∼90 • were randomly selected from the combined set. The DFT optimized geometries were found to be in strong agreement (e.g., within a mean absolute deviation of 1.54 • ) with the GFN2 torsion angles. Such compounds include steric constraints restricting the torsion to be ∼90 • , as illustrated by Figure . We compared ten random patterns with obvious subpopulations (e.g., 90 • in Fig. ), including patterns 10, 23, 48, 53, 125, 149, 216, 253, 270, and 306. For each pattern, five molecules were selected, with the exception of pattern 23, which had only one molecule in the subpopulation. As illustrated in Figure , overall absolute torsion angle deviations between the GFN2-optimized and ωB97X-D/def2-SVP optimized geometries were between 0-5 • , with the median absolute deviation of 2.89 • , and a mean absolute deviation of 4.88 • .