Extension of Density-Corrected Density Functional Theory to Solid-State Calculations: Surface Interaction & Molecular Crystal

Over the decades, density functional approximations (DFAs) have evolved to solve various electronic structure problems. In solid-state systems where long-range interactions are of importance, van der Waals density functionals (vdW-DFs) or DFAs with dispersion corrections (e.g., DFT-D4) are widely used. However, the failure of DFA to predict long-range interactions is addressed by the inclusion of an additional dispersion correction, which often results in an overestimation of energy. Here, we introduce another novel branch that offers accurate prediction for surface interactions and cohesive energy in molecular crystals. In cases where DFAs underestimate the long-range interactions and the additional dispersion correction rather leads to overestimation, our density- and dispersion-corrected density functional theory (D²C-DFT) demonstrates superior performance. For ten ice polymorphs, D²C-DFT predicts cohesive energy with an error of much less than 1 kcal/mol, which is half of the error associated with DFT-D4 predictions. Furthermore, for CO molecules adsorbed on NaCl(100) surface, D²C-DFT accurately predicts both the adsorption energy and the structure. This study explores the potential for the application of DC-DFT to solid-state calculations.