Library of dispersion-corrected atom-centered potentials for generalized gradient approximation functionals: Elements H, C, N, O, He, Ne, Ar, and Kr

Parameters for analytical dispersion-corrected atom-centered potentials (DCACPs) are presented to improve the description of London dispersion forces within the generalized gradient approximation functionals BLYP, BP, and PBE. A library of DCACPs for hydrogen, carbon, nitrogen, oxygen, helium, neon, argon, and krypton was obtained by calibrating against high-level CCSD(T) or configuration interaction references. The performance and transferability of DCACPs were tested on weakly bound complexes and provide excellent results throughout all investigated systems.

Figure 1

The radial term of DCACPs complementing the BLYP functional plotted in the form of $-{\mid {\sigma }_1\mid }^{1∕2}{p}_{l=3}\left(r\right)$.

Figure 2

Interaction energy curve of parallel ${\mathrm{H}}_2$ dimers as a function of intermolecular distance showing the effect of including the midpoint term in the penalty functional.

Figure 3

Interaction energy curves of the sandwich benzene dimer as a function of intermolecular distance with (a) pure and (b) DCACP-augmented GGA functionals.

Figure 4

Graphs showing $\Delta \left(z\right)=\int dxdy[n^{\mathrm{DCACP}}\left(\mathbf{r}\right)-n^{\mathrm{BLYP}}\left(\mathbf{r}\right)]$ [atomic units (a.u.)] against the intermolecular axis $z$ (Å) for the benzene dimer (left) and the ${\mathrm{H}}_2$ dimer (right). The dotted lines show the position of the moieties. The inset shows the DCACP-BLYP electron density for the respective system.