Another interesting example of erroneous behavior in the D4 scheme is observed in complexes of Li + with π-conjugated systems. To illustrate this, we selected two common aromatic hydrocarbons: benzene and naphthalene. The correct local minimum geometries of the associated complexes are shown in Figure . In both cases, the equilibrium distance of Li + from the center of the C 6 ring is approximately 1.8 Å, and this distance remains consistent across both molecules. However, when the Li atom is initially placed far from the ring, it can converge to an artificial second-order stationary point (Fig. ), characterized by two imaginary frequencies corresponding to displacements of the Li atom perpendicular to the axis connecting Li and the center of the C 6 ring. Excluding the D4 correction from the calculations leads to the correct local-minima geometries regardless of the initial position of the Li atom. This artifact can be explained by examining the restricted potential energy scans shown in Figures and. As seen from the CAM-B3LYP-D4 plots (blue line), there are two distinct kinks. The first kink, occurring at a distance of approximately 2.1 Å, is relatively small and does not lead to an artificial minimum. This kink is associated with a step change in the Li-C C 6 coefficient when transitioning from a coordination number of 3 to 2.5. The second kink, more pronounced and resulting in an actual minimum, appears at 2.6 Å. This kink is due to a sharp change in the Li-C C 6 coefficient when transitioning from CN Li = 1 to CN Li = 0, coupled with a step change in the carbon-carbon and carbonhydrogen C 6 coefficients when transitioning from CN C = 4 to 3. The latter factor has the most significant impact on the presence of the kink since there are twelve C-C and C-H atom combinations with short distances that dominate the dispersion energy. As demonstrated in Figure , both the D4S and D4SL schemes successfully eliminate the artificial minimum and correct this issue, although the PES still possesses a slight curvature artifact. We would like to note that even though the proposed solutions could cure cases when the artifact arises from the sharp changes of C 6 coefficients, it is still struggling with the cases in which the coordination number itself rapidly changes as illustrated with the simultaneous dissociation of benzene rings from [K(C 6 H 6 ) 2 ] + complex (Figure ).