To investigate whether the hemibonded structures in the periodic PBE0 + D3 simulations represent transient fluctuations or genuine inherent structures, we selected several snapshots from different parts of the s OH distribution and then quenched (optimized) these structures in non-periodic calculations, including all water molecules within 5.5 Å around the radical and using dielectric continuum boundary conditions. Results of PBE0 + D3/ 6-31G* optimizations (Figs. and) do not suggest any consistent outcome to these quenches; configurations that start off hemibonded (s OH < 0.95) sometimes spinlocalize upon optimization, but in other cases structures that are not initially hemibonded begin to exhibit spin leakage upon optimization. This suggests that there are indeed local minima that correspond to hemibonded solvation motifs at the PBE0 + D3 level of theory.