Computational investigation of van der Waals corrections in the adsorption properties of molecules on the Cu(111) surface.

Here, we report a computational investigation on the role of the most common van der Waals (vdW) corrections (D2, D3, D3(BJ), TS, TS+SCS, TS+HI, and dDsC) employed in density functional theory (DFT) calculations within local and semilocal exchange-correlation functionals to improve the description of the interaction between molecular species and solid surfaces. For this, we selected several molecular model systems, namely, the adsorption of small molecules (CH, CH, CO, CO, HO, and OH) on the close-packed Cu(111) surface, which bind chemisorption or physisorption mechanisms. As expected, we found that the addition of the vdW corrections enhances the energetic stability of the Cu bulk in the face-centered cubic structure, which contributes to increasing the magnitude of the mechanical properties (elastic constants, bulk, Young, and shear modulus).