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

GARCIA, JAVIER; SZALEWICZ, KRZYSZTOF

JOURNAL OF PHYSICAL CHEMISTRY A

AMER CHEMICAL SOC

Año: 2020 vol. 124 p. 1196 - 1203

1089-5639

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, HFDasc(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.