Dispersion Energies with the i-DMFT Method.

Abstract

The recently proposed i-DMFT method [Wang and Baerends, Phys. Rev. Lett. 128, 013001 (2022)] has been proven to be ideally suited to recover strong static correlation in dissociating covalent bonds. Here, the application to van der Waals bonding is investigated using the prototype van der Waals systems triplet H2 and ground-state He2. It is demonstrated that the i-DMFT orbitals are in this case essentially different from the natural orbitals, and the i-DMFT occupations differ substantially from the NO occupations. This is shown to lead to rather deficient interaction potential curves, even if a reasonable well depth may be obtained by fitting of parameters. If the basis set is extended, however, it may no longer be possible to generate van der Waals bonding at all. The linear behavior of the two-electron cumulant energy Ecum as a function of the "entropy" S along a dissociation coordinate, which was the basis of i-DMFT, is distinctly poorer in the case of van der Waals bonding than for covalent bonding.