A (Nearly) Universally Applicable Method for Modeling Noncovalent Interactions Using B3LYP

Abstract

B3LYP is the most widely used density-functional theory (DFT) approach because it is capable of accurately predicting molecular structures and other properties. However, B3LYP is not able to reliably model systems in which noncovalent interactions are important. Here we present a method that corrects this deficiency in B3LYP by using dispersion-correcting potentials (DCPs). DCPs are utilized by simple modifications to input files and can be used in any computational package that can read effective-core potentials. Therefore, the technique requires no programming. DCPs (developed for H, C, N, and O) produce the best results when used in conjunction with 6-31+G(2d,2p) basis sets. The B3LYP-DCP approach was tested on the S66, S22, and HSG-A benchmark sets of noncovalently interacting dimers and trimers and was found to, on average, significantly outperform almost all other DFT-based methods that were designed to treat van der Waals interactions. Users of B3LYP who wish to model systems in which noncovalent interactions (viz., steric repulsion, hydrogen bonding, π-stacking) are present, should consider B3LYP-DCP.

Dispersion corrected DFT approaches for anharmonic vibrational frequency calculations: nucleobases and their dimers

“…Functions are local (l = p for H and l = f for C, N, O) or are semilocal (l = s for H and l = s, p, or d for C, N, O), and operate on electron density in specific angular momentum channels. The DCPs used in this work were developed by optimizing c li and ξ li values such that the error in the predicted interactions chosen from a set of noncovalently bonded dimers (the "fitting" set) was minimized relative to those obtained by CCSD(T)/CBS-quality methods 122 .…”

“…In particular, the DFT-D3 approach, which is the last refined version of DFT-D 110,123,124 parameterized for the 94 elements of the periodic table, has been used successfully to describe tripeptide-folding, metallic systems, graphene, benzene on the Ag(111) surface and other molecular complexes 111 . Then, the recently proposed B3LYP-DCP method (developed for H, C, N, and O), which corrects B3LYP by using atomcentered effective core potentials (dispersion-correcting potentials -DCPs) composed of Gaussian-type functions [119][120][121] , is able to model satisfactorily π-stacking, steric repulsion noncovalent interactions and also hydrogen bonding 122 .…”

First principles view on chemical compound space: Gaining rigorous atomistic control of molecular properties

“…[29] The manipulation of pseudopotentials for affecting electronic structure properties is nothing out of the ordinary. It has successfully been deployed for an array of properties including relativistic effects, [30] self-interaction corrections, [31,32] exact-exchange and quantum mechanical/molecular mechanical (QM/MM) boundary effects, [33,34] van-derWaals interactions, [35,36] and widening the band gap. [37,38,39] For fractional nuclear charges, we can interpolate pseudopotentials, and evaluate properties as a function of order parameter, 0 k 1.…”

Problems, successes and challenges for the application of dispersion-corrected density-functional theory combined with dispersion-based implicit solvent models to large-scale hydrophobic self-assembly and polymorphism

“…[18] Further, it has now been established that even highly-parameterised functionals [19,20] do not describe the asymptotes of the London-dispersion energy correctly and that they still suffer from the same underlying problem as all conventional DFT approximations. [21] In the last decade, other promising approaches have been developed to tackle the dispersion problem, and they can be divided into three categories: van-der-Waals density functionals (vdW-DFs), [22,23,24,25] effective-core potentials (ECPs) that try to mimic dispersion effects, [26,27,28,29,30] and additive dispersion corrections. [31,32,33,34,35,36,37,38,39,40,41,42] Herein, we briefly outline only the most important aspects of these corrections; for detailed reviews of the advantages and disadvantages of the different approaches we refer the reader to Refs.…”

“…[26,27,28,29,30] The technical advantage of these methods is that ECPs are implemented in all standard quantum-chemistry codes and that they can be readily used. A disadvantage is that the potentials have to be fitted for every single element, which limits the variety of systems that can be treated with such methods.…”