Basis set convergence of explicitly correlated double-hybrid density functional theory calculations

Amir Karton, J.M.L. Martin

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29 Citations (Scopus)
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Abstract

The basis set convergence of explicitly correlated double-hybrid density functional theory(DFT) is investigated using the B2GP-PLYP functional. As reference values, we use basis set limit B2GP-PLYP-F12 reaction energies extrapolated from the aug′-cc-pV(Q+d)Z and aug′-cc-pV(5+d)Z basis sets. Explicitly correlated double-hybrid DFT calculations converge significantly faster to the basis set limit than conventional calculations done with basis sets saturated up to the same angular momentum (typically, one “gains” one angular momentum in the explicitly correlated calculations). In explicitly correlated F12 calculations the VnZ-F12 basis sets converge faster than the orbital A′VnZ basis sets. Furthermore, basis set convergence of the MP2-F12 component is apparently faster than that of the underlying Kohn-Sham calculation. Therefore, the most cost-effective approach consists of combining the MP2-F12 correlation energy from a comparatively small basis set such as VDZ-F12 with a DFT energy from a larger basis set such as aug′-cc-pV(T+d)Z.
Original languageEnglish
Pages (from-to)144119
JournalJournal of Chemical Physics
Volume135
Issue number14
Early online date13 Oct 2011
DOIs
Publication statusPublished - 14 Oct 2011

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