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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

Abstract

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 amore » 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.« less

Authors:
 [1];  [2];  [1]; ORCiD logo [1]
  1. ORNL
  2. Georgia Institute of Technology, Atlanta
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1006468
DOE Contract Number:  
AC05-00OR22725
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 134; Journal Issue: 8; Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 97 MATHEMATICAL METHODS AND COMPUTING; DENSITY FUNCTIONAL METHOD; INTERACTIONS; MOLECULES; COMPLEXES; PROTEINS; LIGANDS; CHEMICAL BONDS; DISSOCIATION

Citation Formats

Burns, Lori, Sherrill, David, Vazquez Mayagoitia, Alvaro, and Sumpter, Bobby G. Density-functional approaches to non-bonding interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals. United States: N. p., 2011. Web. doi:10.1063/1.3545971.
Burns, Lori, Sherrill, David, Vazquez Mayagoitia, Alvaro, & Sumpter, Bobby G. Density-functional approaches to non-bonding interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals. United States. https://doi.org/10.1063/1.3545971
Burns, Lori, Sherrill, David, Vazquez Mayagoitia, Alvaro, and Sumpter, Bobby G. Tue . "Density-functional approaches to non-bonding interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals". United States. https://doi.org/10.1063/1.3545971.
@article{osti_1006468,
title = {Density-functional approaches to non-bonding interactions: a comparison of dispersion corrections (DFT-D), exchange-hole dipole moment (XDM) theory, and specialized functionals},
author = {Burns, Lori and Sherrill, David and Vazquez Mayagoitia, Alvaro and Sumpter, Bobby G.},
abstractNote = {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.},
doi = {10.1063/1.3545971},
url = {https://www.osti.gov/biblio/1006468}, journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 8,
volume = 134,
place = {United States},
year = {2011},
month = {2}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996


An efficient algorithm for the density-functional theory treatment of dispersion interactions
journal, March 2009


Further analysis and comparative study of intermolecular interactions using dimers from the S22 database
journal, January 2009


Scaled MP3 Non-Covalent Interaction Energies Agree Closely with Accurate CCSD(T) Benchmark Data
journal, January 2009


Basis set dependence of the doubly hybrid XYG3 functional
journal, September 2010


Dispersion-corrected Mo̸ller–Plesset second-order perturbation theory
journal, January 2009


Exchange-hole dipole moment and the dispersion interaction revisited
journal, October 2007


Exchange-hole dipole moment and the dispersion interaction
journal, April 2005


Density Functionals with Broad Applicability in Chemistry
journal, February 2008


Quantum Chemical Benchmark Energy and Geometry Database for Molecular Clusters and Complex Molecular Systems (www.begdb.com): A Users Manual and Examples
journal, January 2008


Semiempirical hybrid density functional with perturbative second-order correlation
journal, January 2006


Optimization of Effective Atom Centered Potentials for London Dispersion Forces in Density Functional Theory
journal, October 2004


On the Structure and Geometry of Biomolecular Binding Motifs (Hydrogen-Bonding, Stacking, X−H···π): WFT and DFT Calculations
journal, December 2009


Efficient Diffuse Basis Sets for Density Functional Theory
journal, February 2010


Highly Accurate CCSD(T) and DFT-SAPT Stabilization Energies of H-Bonded and Stacked Structures of the Uracil Dimer
journal, August 2008


Ab Initio Calculation of Nonbonded Interactions:  Are We There Yet?
journal, July 2000


Jacob’s ladder of density functional approximations for the exchange-correlation energy
conference, January 2001


van der Waals Interactions in Density-Functional Theory: Intermolecular Complexes
journal, March 2010


Investigations on C–H⋯π interactions in RNA binding proteins
journal, August 2007


Interactions with Aromatic Rings in Chemical and Biological Recognition
journal, March 2003


Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992


Efficient computation of the dispersion interaction with density-functional theory
journal, April 2009


Oscillations in meta-generalized-gradient approximation potential energy surfaces for dispersion-bound complexes
journal, July 2009


Cumulative π-π interaction triggers unusually high stabilization of linear hydrocarbons inside the single-walled carbon nanotube
journal, January 2007


A fifth-order perturbation comparison of electron correlation theories
journal, May 1989


Accurate description of van der Waals complexes by density functional theory including empirical corrections
journal, January 2004


Long-range corrected double-hybrid density functionals
journal, November 2009


Assessment of the Performance of DFT and DFT-D Methods for Describing Distance Dependence of Hydrogen-Bonded Interactions
journal, December 2010


Van der Waals density functional theory with applications: Van Der Waals DFT
journal, October 2004


Basis-set convergence in correlated calculations on Ne, N2, and H2O
journal, April 1998


Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics
journal, March 2009


Perturbation Theory Approach to Intermolecular Potential Energy Surfaces of van der Waals Complexes
journal, November 1994


Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability
journal, January 2007


A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu
journal, April 2010


Doubly Hybrid Meta DFT:  New Multi-Coefficient Correlation and Density Functional Methods for Thermochemistry and Thermochemical Kinetics
journal, May 2004


Exchange-hole dipole moment and the dispersion interaction: High-order dispersion coefficients
journal, January 2006


Long-range corrected hybrid density functionals with damped atom–atom dispersion corrections
journal, January 2008


Benchmark Databases for Nonbonded Interactions and Their Use To Test Density Functional Theory
journal, March 2005


Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993


Empirically corrected DFT and semi-empirical methods for non-bonding interactions
journal, January 2010


Assessment of Gaussian-3 and density functional theories for a larger experimental test set
journal, May 2000


Highly Accurate Coupled Cluster Potential Energy Curves for the Benzene Dimer:  Sandwich, T-Shaped, and Parallel-Displaced Configurations
journal, November 2004


Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
journal, January 1988


An Assessment of Density Functional Methods for Potential Energy Curves of Nonbonded Interactions: The XYG3 and B97-D Approximations
journal, February 2010


Performance of spin-component-scaled Møller–Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions
journal, January 2007


Advances in methods and algorithms in a modern quantum chemistry program package
journal, January 2006


On the exchange-hole model of London dispersion forces
journal, July 2007


Exchange holes in inhomogeneous systems: A coordinate-space model
journal, April 1989


Comparative Study of Selected Wave Function and Density Functional Methods for Noncovalent Interaction Energy Calculations Using the Extended S22 Data Set
journal, July 2010


Toward reliable density functional methods without adjustable parameters: The PBE0 model
journal, April 1999


Assessment of the Perdew–Burke–Ernzerhof exchange-correlation functional
journal, March 1999


?-? Interactions in Self-Assembly
journal, May 1997


Dispersion interactions in density-functional theory
journal, December 2009


Understanding of Assembly Phenomena by Aromatic−Aromatic Interactions:  Benzene Dimer and the Substituted Systems
journal, May 2007


Assessment of Gaussian-2 and density functional theories for the computation of enthalpies of formation
journal, January 1997


Effects of Heteroatoms on Aromatic π−π Interactions: Benzene−Pyridine and Pyridine Dimer
journal, February 2009


Basis set consistent revision of the S22 test set of noncovalent interaction energies
journal, April 2010


Semiempirical GGA-type density functional constructed with a long-range dispersion correction
journal, January 2006


Empirical correction to density functional theory for van der Waals interactions
journal, January 2002


Assessment of the Performance of the M05−2X and M06−2X Exchange-Correlation Functionals for Noncovalent Interactions in Biomolecules
journal, November 2008


Supramolecular Polymers
journal, December 2001


Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions
journal, June 2005


Improvement of the coupled-cluster singles and doubles method via scaling same- and opposite-spin components of the double excitation correlation energy
journal, March 2008


Derivation of the dispersion energy as an explicit density- and exchange-hole functional
journal, February 2009


Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities
journal, July 1998


Van der Waals Interactions in Density-Functional Theory: Rare-Gas Diatomics
journal, March 2009


Density Functionals for Noncovalent Interaction Energies of Biological Importance
journal, December 2006


Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994


Density-functional thermochemistry. V. Systematic optimization of exchange-correlation functionals
journal, November 1997


A System-Dependent Density-Based Dispersion Correction
journal, June 2010


Nonlocal van der Waals Density Functional Made Simple
journal, August 2009


Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs
journal, January 2006


Application of 25 density functionals to dispersion-bound homomolecular dimers
journal, August 2004