Intermolecular forces from asymptotically corrected density functional description of monomers

摘要: Abstract Symmetry-adapted perturbation theory based on Kohn–Sham determinants, SAPT(KS), was shown before to perform poorly for the electrostatic energy which is potentially exact in this approach. We demonstrate that some deficiencies of SAPT(KS) result from wrong asymptotics exchange-correlation potentials. On applying an asymptotic correction, we were not only able recover electrostatics, but also first-order exchange and second-order induction exchange-induction energies fairly accurate. Dispersion still reproduced can be computed reasonably accurately damped expansion.