Ab Initio Extended Hartree-Fock plus Dispersion Method Applied to Dimers with Hundreds of Atoms

The Hartree-Fock plus dispersion plus first-order correlation (HFDc⁽¹⁾) method consists in augmenting the HF interaction energy by the correlation part of the first-order interaction energy and the second-order dispersion and exchange-dispersion energies. All of the augmentation terms are computed using the symmetry-adapted perturbation theory based on density functional theory description of monomers [SAPT(DFT)]; thus, HFDc⁽¹⁾ is a fully ab initio method. A partly empirical version of this method, HFD_asc⁽¹⁾, uses a damped asymptotic expansion for the dispersion plus exchange-dispersion term fitted to SAPT(DFT) ab initio values. The HFDc⁽¹⁾ interaction energies for dimers in the S22, S66, S66x8, NCCE31, IonHB, and UD-ARL benchmark data sets are more accurate than those given by most ab initio methods with comparable costs. HFDc⁽¹⁾ can be used routinely for dimers with nearly 200 atoms, such as included in the S12L benchmark set, giving results comparable to those obtained by the most expensive methods applicable.