Smoother Semiclassical Dispersion for Density Functional Theory via D3S: Understanding and Addressing Unphysical...

One of the most widely used and computationally efficient models that accounts for London dispersion interactions within density functional theory (DFT) is the D3 dispersion correction model. In this work, we demonstrate that this model can induce the appearance of unphysical minima on the potential energy surface (PES) when the coordination number of atoms changes. Optimizing to these artifactual structures can lead to significant errors in determining the interaction energy between two molecules and in estimating the thermodynamic properties of the system. In several specific examples, such as Kuratowski-type H₂-NiKur and H₂-PdKur clusters, these local minima exhibited extremely high PES curvature, resulting in incorrect estimations of harmonic frequencies and significant overestimations of zero-point energy and enthalpy values. Although such erroneous behavior of the D3 model is relatively rare, it can occur across a wide range of chemical species, including molecules like the [Li(C₆H₆)]⁺ complex and the dispiro(acridan)-substituted pyracene (DSAP) molecule. Our analysis reveals that the root of the problem lies in the definition of the AB atomic-pair dependent C₆^AB coefficients in the D3 model. To address this issue, we propose a reparameterization of the D3 model by introducing a modified C₆^AB functional form that now depends on the specific pair of considered atoms. This new model, termed D3-Smooth (or D3S for short), is designed to smooth out the PES associated with the dispersion correction. By doing so, we demonstrate that D3S eliminates unphysical local minima while maintaining the quite satisfactory accuracy of the parent D3 method in interaction energy benchmark sets. For example, the RMS difference between using the D3(BJ) correction to B3LYP and the D3S(BJ) correction across the large MGCDB84 data set of nearly 5000 data points is only 0.12 kJ/mol. Similar results are obtained for every other D3-corrected functional tested. Consistent with this result, no significant improvement could be obtained for the B3LYP-D3S(0) correction by reoptimizing the damping function.