In view of the close association of the small-r O * O peak with the hemibond, it is easy to see how one might conclude from the T = 370 K data in Fig. that the hemibond is absent in these simulations, since semilocal functionals such as BLYP produce a much more pronounced feature, closer to the BLYP + D3 result obtained from QM/MM simulations (Fig. ). This leaves open the possibility that the hemibond could be a rare event or a transient fluctuation. However, the appearance of a small-r O * O feature at lower temperature suggests that the hemibond instead corresponds to a local minimum on the potential energy surface, i.e., an "inherent structure". We will return to this issue below.