Dispersion corrections improve the accuracy of both noncovalent and covalent interactions energies predicted by a density-functional theory approximation

Download
  1. (PDF, 702 KB)
  2. Get@NRC: Dispersion corrections improve the accuracy of both noncovalent and covalent interactions energies predicted by a density-functional theory approximation (Opens in a new window)
DOIResolve DOI: http://doi.org/10.1021/acs.jpca.5b02809
AuthorSearch for: ; Search for:
TypeArticle
Journal titleJournal of Physical Chemistry A
ISSN1089-5639
Volume119
Issue25
Pages67036713; # of pages: 11
SubjectBinding energy; Chemical bonds; Chemical properties; Computation theory; Dispersions; Bond dissociation enthalpies; Computational costs; Covalent interactions; Density functionals; Diels-Alder reaction; Dispersion correction; Generalized gradient approximations; Radical stabilization energy; Density functional theory
AbstractThe use of pairwise dispersion corrections together with dispersion-correcting potentials (DCPs) offers a computationally low-cost approach to improving the performance of a density-functional theory based method with respect to the prediction of important chemical properties. In this work, we develop DCPs for the C, H, N, and O atoms for use with the BLYP generalized gradient approximation functional coupled with "D3" pairwise dispersion corrections and 6-31+G(2d,2p) basis sets. The combined approach, referred to as BLYP-D3-DCP, offers generally improved performance over both unadorned BLYP and BLYP with D3 corrections with respect to the prediction of noncovalent binding energies (BEs) and covalent bond dissociation enthalpies (BDEs). Predicted barrier heights for a set of pericyclic and Diels-Alder reactions are improved in some instances, as are organic bond separation reaction energies and radical stabilization energies. It is also shown that the BLYP-D3-DCP approach outperforms B3LYP-D3 in the prediction of many chemical properties, in particular noncovalent BEs and BDEs, suggesting that the addition of D3 and DCP corrections, which have negligible computational cost, to simple density functionals like BLYP may elevate their performance to that of more complex functionals such as B3LYP.
Publication date
PublisherAmerican Chemical Society
LanguageEnglish
AffiliationNational Research Council Canada (NRC-CNRC); National Institute for Nanotechnology
Peer reviewedYes
NPARC number21276943
Export citationExport as RIS
Report a correctionReport a correction
Record identifier1c9309da-f34d-412f-8c7d-d68c53d10fa0
Record created2015-11-10
Record modified2016-05-09
Bookmark and share
  • Share this page with Facebook (Opens in a new window)
  • Share this page with Twitter (Opens in a new window)
  • Share this page with Google+ (Opens in a new window)
  • Share this page with Delicious (Opens in a new window)