Density-functional approaches to noncovalent interactions: A comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals

Abstract

A systematic study of techniques for treating noncovalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength compiled for molecular complexes of diverse size and nature. In particular, the efficacy of functionals deliberately crafted to encompass long-range forces, a posteriori DFT+dispersion corrections (DFT-D2 and DFT-D3), and exchange-hole dipole moment (XDM) theory is assessed against a large collection (469 energy points) of reference interaction energies at the CCSD(T) level of theory extrapolated to the estimated complete basis set limit. The established S22 [revised in J. Chem. Phys. 132, 144104 (2010)] and JSCH test sets of minimum-energy structures, as well as collections of dispersion-bound (NBC10) and hydrogen-bonded (HBC6) dissociation curves and a pairwise decomposition of a protein-ligand reaction site (HSG), comprise the chemical systems for this work. From evaluations of accuracy, consistency, and efficiency for PBE-D, BP86-D, B97-D, PBE0-D, B3LYP-D, B970-D, M05-2X, M06-2X, ωB97X-D, B2PLYP-D, XYG3, and B3LYP-XDM methodologies, it is concluded that distinct, often contrasting, groups of these elicit the best performance within the accessible double-ζ or robust triple-ζ basis set regimes and among hydrogen-bonded or dispersion-dominated complexes. For overall results, M05-2X, B97-D3, and B970-D2 yield superior values in conjunction with aug-cc-pVDZ, for a mean absolute deviation of 0.41 - 0.49 kcal/mol, and B3LYP-D3, B97-D3, ωB97X-D, and B2PLYP-D3 dominate with aug-cc-pVTZ, affording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 - 0.38 kcal/mol.

SCAN-based hybrid and double-hybrid density functionals from models without fitted parameters

“…Nonetheless, as SCAN and PBE are both semilocal functionals, they cannot adequately describe the van der Waals (vdW) asymptote [10,15], which requires an accurate treatment of long-range dynamical correlation effects. Incorporating SCAN and PBE with the double-hybrid schemes [38][39][40][41][42][43][44][45][46][47][48][49][50][51][52][53][54][55], the DFT-D (KS-DFT with empirical dispersion corrections) schemes [44,[82][83][84][85][86][87][88], or fully nonlocal density functionals [89][90][91] may greatly improve the accuracy of SCAN and PBE for vdW interactions. Among the functionals examined on the S22 and S66 sets, SCAN0-2 ranks first, while SCAN-QIDH and PBE0-2 rank second and third, respectively.…”

Rubrene: The Interplay between Intramolecular and Intermolecular Interactions Determines the Planarization of Its Tetracene Core in the Solid State

“…DFT analyses of the neutral ground states were carried out using a variety of density functionals containing empirically parameterized dispersion interactions that were found to perform well in a previous benchmark study: 28 B3LYP and B3LYP-D, [23][24][25] IP-tuned ωB97 and ωB97-D, 29 Tables S1 and S2 in the SI). All geometry optimizations were performed with the cc-pVDZ basis set.…”

Role of exact exchange in thermally-assisted-occupation density functional theory: A proposal of new hybrid schemes

“…Accordingly, KS-DFAs and hybrid functionals may be combined with the DFT-D (KS-DFT with empirical dispersion corrections) schemes [17,[36][37][38][39][40] and the double-hybrid (mixing both the HF exchange energy and the second-order Møller-Plesset (MP2) correlation energy [41] into KS-DFAs) schemes [30,33,42], showing an overall satisfactory accuracy for the NCIE problems.…”