Benchmarking several van der Waals dispersion approaches for the description of intermolecular interactions.

Seven methods, including three van der Waals density functionals (vdW-DFs) and four different variants of the Tkatchenko-Scheffler (TS) methods, are tested on the A24, L7, and Taylor et al.'s "blind" test sets. It is found that for these systems, the vdW-DFs perform better that the TS methods. In particular, the vdW-DF-cx functional gives binding energies that are the closest to the reference values, while the many-body correction of TS does not always lead to an improvement in the description of molecular systems. In light of these results, several directions for further improvements to describe van der Waals interactions are discussed.

Improving the Efficiency of Beyond-RPA Methods within the Dielectric Matrix Formulation: Algorithms and Applications to the A24 and S22 Test Sets.

Within a formalism based on dielectric matrices, the electron-hole time-dependent Hartree-Fock (eh-TDHF) and the adiabatic connection second-order screened exchange (AC-SOSEX) are promising approximations to improve ground-state correlation energies by including exchange effects beyond the random phase approximation (RPA). We introduce here an algorithm based on a Gram-Schmidt orthogonalization (GSO) procedure that significantly reduce the number of matrix elements to be computed to evaluate the response functions that enter in the formulation of these two methods. By considering the A24 test set, we show that this approach does not lead to a significant loss of accuracy and can be effectively applied to compute the small interaction energies involved in weakly bound dimers. Importantly, the GSO method significantly extends the applicability of the eh-TDHF and AC-SOSEX to large systems. This is shown by considering the S22 test set, which includes dimers with up to one hundred valence electrons requiring hundreds of thousands of plane-waves in the basis set. By comparing our results to coupled-cluster benchmark values, we show that the inclusion of exchange effects beyond the RPA significantly improves the accuracy, with mean absolute errors that decrease by almost 40% for the A24 test set and by almost 50% for the S22 test set. This approach based on dielectric matrices is particularly suited for plane-wave implementations and might be used in the future to improve the description of the correlation energy in solid state applications.

Communication: A novel implementation to compute MP2 correlation energies without basis set superposition errors and complete basis set extrapolation.

By using a formulation based on the dynamical polarizability, we propose a novel implementation of second-order Møller-Plesset perturbation (MP2) theory within a plane wave (PW) basis set. Because of the intrinsic properties of PWs, this method is not affected by basis set superposition errors. Additionally, results are converged without relying on complete basis set extrapolation techniques; this is achieved by using the eigenvectors of the static polarizability as an auxiliary basis set to compactly and accurately represent the response functions involved in the MP2 equations. Summations over the large number of virtual states are avoided by using a formalism inspired by density functional perturbation theory, and the Lanczos algorithm is used to include dynamical effects. To demonstrate this method, applications to three weakly interacting dimers are presented.