In the CVS-0 X2PA spectrum, many of these same transitions are important along with XA 1 → c1A 1 at 287.0 eV, XA 1 → c2A 1 at 287.9 eV, XA 1 → c5A 1 at 288.7 eV, XA 1 → c7A 1 at 288.8 eV, XA 1 → c12A 1 at 289.4 eV, XA 1 → c2B 1 at 287.9 eV, and XA 1 → c5B 1 at 288.7 eV. The CVS-uS spectrum, in contrast, is a little less rich with only the XA 1 → c1A 1 , XA 1 → c2A 1 , XA 1 → c5A 1 , XA 1 → c8A 1 (at 288.9 eV), XA 1 → c14A 1 (at 289.6 eV), XA 1 → c19A 1 (at 290.3 eV), XA 1 → c20A 1 , and XA 1 → c15B 1 transitions dominant. pNA, therefore, represents yet another system that features a large valence contribution to the X2PA cross sections, highlighting the importance of including the valence resolvent in our model. The most dominant transition in the CVS-uS spectrum, XA 1 → c1A 1 and XA 1 → c2A 1 , are characterized by different pairs of a 1 → a 1 and b 1 → b 1 orbital transitions, and are of σ * /Rydberg type. For the former, the core hole is delocalized on the carbons meta to the amine group, whereas for the latter, the core hole is predominantly centered on the carbons meta to the nitro group. The next dominant XA 1 → c20A 1 transition is characterized by a a 1 → a 1 transition with the core hole on the carbon atom connected to the nitro group, see Table in the SI.