Structural quenches of the periodic PBE0 + D3 trajectories suggest that the hemibond is an inherent structure at this level of theory. When the same structures are relaxed at the (SIE-free) MP2 level of theory, the unpaired spin localizes on the hydroxyl moiety and thus the traditional 2c-3e hemibond disappears, yet a "pseudo-hemibond" persists, characterized by an O * • • • O close-contact with no hydrogen bond. This appears to be enough to facilitate an intense 1b 2 (H 2 O) → 2p( OH) charge-transfer transition at an excitation energy that is consistent with the experimental UV spectrum of OH(aq). No excitation energies consistent with experiment can be found in hydrogen-bonded geometries.