Low-Cost Quantum Chemical Methods for Noncovalent Interactions

Abstract

The efficient and reasonably accurate description of noncovalent interactions is important for various areas of chemistry, ranging from supramolecular host-guest complexes and biomolecular applications to the challenging task of crystal structure prediction. While London dispersion inclusive density functional theory (DFT-D) can be applied, faster "low-cost" methods are required for large-scale applications. In this Perspective, we present the state-of-the-art of minimal basis set, semiempirical molecular-orbital-based methods. Various levels of approximations are discussed based either on canonical Hartree-Fock or on semilocal density functionals. The performance for intermolecular interactions is examined on various small to large molecular complexes and organic solids covering many different chemical groups and interaction types. We put the accuracy of low-cost methods into perspective by comparing with first-principle density functional theory results. The mean unsigned deviations of binding energies from reference data are typically 10-30%, which is only two times larger than those of DFT-D. In particular, for neutral or moderately polar systems, many of the tested methods perform very well, while at the same time, computational savings of up to 2 orders of magnitude can be achieved.

First principles investigation of hydrogen physical adsorption on graphynes' layers

“…The Blöchl all-electron projector-augmented wave (PAW) method [28,29], with an energy cutoff of 750 eV and a 2s 2 2p 2 electron valence potential for carbon, has been employed. A periodic model has been considered with an initial supercell system for the graphtriyne isolated The computed energies have been corrected by two-and three-body dispersion contributions including the Becke-Johnson damping scheme [30] and an Axilrod-Teller-Muto threebody term [31], as implemented in the df td3 program of Grimme et al [32].…”

Conformative alignment of isoquinolinyl substituents at the resorcinarene rim

“…23,34 For the calculations of harmonic vibrational frequencies and subsequent evaluation of thermostatistical correction from interaction (complexation) energy DE to Gibbs free energy DG, the semiempirical DFTB tight-binding method was employed (for an overview on its performance for non-covalent interactions see Ref. 35). Low-lying vibrational modes were treated in a special rotor-approximation to avoid numerical artifacts from the (harmonically computed) vibrational entropies, see Ref.…”

Theoretical description of 2D-cluster formation of nonionic surfactants at the air/water interface

“…However, one should keep in mind the above mentioned fact that the PM6 and PM7 methods underestimate the length of СН···НС bonds. So, their use for estimation of the structural parameters of the unit cells for associates is open to question [73]. Along with the mentioned fact, the semiempirical methods are good candidates for calculation of the structure of van der Waals complexes because of the benefits in the calculation time and system size in comparison to the WFT and DFT methods.…”