Recent development of atom‐pairwise van der waals corrections for density functional theory: From molecules to solids

Abstract

Van der Waals (vdW) interactions are important in numerous physical, chemical, and biological systems. However, traditional density functional theory (DFT) within local or semi-local approximations can hardly treat this interaction. Among various attempts to handle vdW interactions in DFT, semiempirical correction methods are known to present the advantages of low additional computational costs and easy implementation in conventional DFT codes. In this review, we summarize the state-of-the-art semi-empirical vdW correction methods based on pairwise summations within the atoms-inmolecules scaling framework, such as the Grimme's D3 methods and variants of the Tkatchenko-Scheffler method. In addition, we compare the performance of these methods for systems ranging from molecules to solids, which have dispersive to ionic interactions: 128 molecular pairs, 23 molecular crystals, 4 noble gas crystals, 27 two-dimensional layered materials, and 9 ionic crystals.

Multiscale Simulation Method for Quantitative Prediction of Surface Wettability at the Atomistic Level

“…These values show a saturating behavior after the number of layers becomes more than 3–4. This implies that graphene wetting is mainly influenced by the vdW interaction at the interface because the vdW interaction shows a similar saturation behavior upon increasing the number of graphene layers beyond the vdW interaction length scale of ∼10 Å . Indeed, when W ad is compared to the calculated – E int vdW / S , almost the same trend is observed, as shown in Figure S6.…”

“…As a complement to experiments, in such cases, first-principle-based simulation can serve as the most reliable method to provide a theoretical bound for predicting the θ CA values of idealized surface by minimizing all possible ambiguities at the atomic scale. On the basis of quantum mechanics (QM), density functional theory (DFT) rather accurately describes the noncovalent interaction between the solid surface and a liquid molecule, particularly with the recent development of various van der Waal’s corrected DFT methods. − However, because of its high computational cost, DFT calculations are often conducted in a static manner while ignoring the dynamics; as a result, the liquid phase cannot be properly considered. When the dynamics is included in DFT, a formidable computational cost of ab initio molecular dynamics (AIMD) simulations hampers a sufficient sampling of molecular configurations of the liquid phase.…”

Assessment of van der Waals inclusive density functional theory methods for layered electroactive materials

“…63 The RPA method takes into account long-range dynamic correlation effects and is considered as reference for twodimensional materials. 64 In particular, Björkman et al…”

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

“…But although the accuracy of these methods has been scrutinized in the past 5,9,12,[24][25][26][27][28] , it is presently still difficult to have a complete picture of their respective performances. It is thus difficult to make an informed choice about which method to use for a given problem, by trading off speed and accuracy.…”

“…However, one of the most critical failures of standard exchange-correlation functionals is their inability to describe correctly dispersive forces. Recently, efforts to cure this shortcoming have been made at different levels of theory, ranging from: i) corrections to existing semi-local functionals (the so-called family of DFT+D methods) [3][4][5][6][7][8][9] ,ii) functionals taking into account non-locality explicitly [10][11][12] , iii) methods expressing the exchange-correlation contribution in terms of response functions such as the random phase approximation (RPA) and beyond-RPA methods [13][14][15][16][17] , through to iv) advanced wavefunction methods such as coupled cluster and quadratic configuration interaction methods [18][19][20][21][22][23] . The choice of one method over another is usually dictated by the size of the system -although wavefunction methods are often precise, their computational cost makes them impossible to use for systems of a certain size.…”