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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.3545971· OSTI ID:1006468
 [1];  [2];  [1]; ORCiD logo [1]
  1. ORNL
  2. Georgia Institute of Technology, Atlanta
+ Show Author Affiliations

A systematic study of techniques for treating non-covalent interactions within the computationally efficient density functional theory (DFT) framework is presented through comparison to benchmark-quality evaluations of binding strength com- piled for molecular complexes of diverse size and nature. In particular, the effi- cacy of functionals deliberately crafted to encompass long-range forces, a posteri- ori 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 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 conjunc- tion 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, af- fording, together with XYG3/6-311+G(3df,2p), a mean absolute deviation of 0.33 – 0.38 kcal/mol.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE
DOE Contract Number:
AC05-00OR22725
OSTI ID:
1006468
Journal Information:
Journal of Chemical Physics, Vol. 134, Issue 8; ISSN 0021-9606
Country of Publication:
United States
Language:
English

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Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
97 MATHEMATICAL METHODS AND COMPUTING
DENSITY FUNCTIONAL METHOD
INTERACTIONS
MOLECULES
COMPLEXES
PROTEINS
LIGANDS
CHEMICAL BONDS
DISSOCIATION