Assessment of the PW86+PBE+XDM density functional on van der Waals complexes at non-equilibrium geometries

Alya A. Arabi, Axel D. Becke

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15 Citations (Scopus)


The deficiency of conventional density-functional theory (DFT) in properly describing van der Waals (vdW) (especially dispersion-bound) complexes has been extensively addressed in the past decade. There are now several new methods published in the literature that are capable of accurately capturing weak dispersion interactions in complexes at equilibrium geometries. However, the performance of these new methods at non-equilibrium geometries remains to be assessed. We have previously published [F. O. Kannemann and A. D. Becke, J. Chem. Theory Comput. 6, 1081 (2010)10.1021/ct900699r; A. D. Becke, A. A. Arabi, and F. O. Kannemann, Can. J. Chem. 88, 1057 (2010)10.1139/V10-073] that the functional PW86+PBE+XDM for exchange + correlation dispersion, respectively, is a highly accurate functional for general thermochemistry and vdW complexes at equilibrium geometries. Here, we show that this nonempirical, except for two parameters in the dispersion damping part, functional also performs well for vdW complexes at compressed and stretched intermonomer separations. The mean absolute relative error (MARE) is 9.4 overall for vdW complexes in the S22×5 database incorporating compressed and stretched geometries [J. Rezac, K. E. Riley, and P. Hobza, J. Chem. Theory Comput. 7, 2427 (2011)10.1021/ct2002946]. Our largest MARE on the S22×5 database is 13.3 on the compressed geometry set.

Original languageEnglish
Article number014104
JournalJournal of Chemical Physics
Issue number1
Publication statusPublished - Jul 7 2012
Externally publishedYes

ASJC Scopus subject areas

  • General Physics and Astronomy
  • Physical and Theoretical Chemistry


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