Blind test of density-functional-based methods on intermolecular interaction energies

Abstract

In the past decade, a number of approaches have been developed to fix the failure of (semi)local density-functional theory (DFT) in describing intermolecular interactions. The performance of several such approaches with respect to highly accurate benchmarks is compared here on a set of separation-dependent interaction energies for ten dimers. Since the benchmarks were unknown before the DFT-based results were collected, this comparison constitutes a blind test of these methods.

Development of constant-pH simulation methods in implicit solvent and applications in biomolecular systems

“…There is still room for development in sampling techniques, the choice of reaction progress coordinate (Meyer et al 2016), new DFT methods for molecular interactions (Brémond et al 2016;Taylor et al 2016), and so on. Grand challenges are the DFT treatment for colloidal dimension systems as proteins and RNA/DNA or high-level quantum chemistry calculations for medium molecules with inclusion of the solvent sampling.…”

Benchmarking Several van der Waals Dispersion Approaches for the Description of Intermolecular Interactions

“…To further benchmark the methods of interest here on a different dataset, we have chosen the one created by Taylor et al 31 , composed of 10 dimers with a range of sizes (from 6 to 32 atoms). In their work, the authors did not release the reference values before the various calculations were conducted, which therefore constituted a "blind" test.…”

“…Moreover, a majority of dimers of this set are not found in other sets. The geometries used here correspond to the near equilibrium positions, and were taken from the supplementary material of Taylor et al 31 optimized at the MP2/aug-cc-pVTZ level of theory. The reference values for the binding energies have been obtained with CCSD(T) extrapolated to CBS by the same authors 31 .…”

“…In this paper, we provide additional benchmarking on the performance of the Tkatchenko and Scheffler (TS) 6 , non-local van der Waals density functionals (vdW-DFs) and many-body dispersion (MBD) methods on the A24 dataset 29 , the L7 30 dataset, and on a set of dimers recently studied by Taylor et al 31 . These datasets have been chosen to cover a wide range of chemical situations, from purely dispersive interactions to hydrogen bonds.…”

“…II, we briefly present the theoretical formalism of the methods used here. Then the interactions energies, calculated for the A24 test set 29 , the L7 test set 30 and the "blind" set of molecules proposed by Taylor et al 31 , are shown and analyzed in Sec. III.…”