Jump to main content
Jump to site search

Issue 22, 2015
Previous Article Next Article

Subsystem-DFT potential-energy curves for weakly interacting systems

Author affiliations

Abstract

Kohn–Sham density-functional theory (DFT) within the local-density approximation (LDA) or the generalized-gradient approximation (GGA) is known to fail for the correct description of London dispersion interactions. Often, not even bound potential-energy surfaces are obtained for van der Waals complexes, unless special correction schemes are employed. In contrast to that, there has been some evidence for the fact that subsystem-based density functional theory produces interaction energies for weakly bound systems which are superior to Kohn–Sham DFT results without dispersion corrections. This is usually attributed to an error cancellation between the approximate exchange–correlation and non-additive kinetic-energy functionals employed in subsystem DFT. Here, we investigate the accuracy of subsystem DFT for weakly interacting systems in detail, paying special attention to the shape of the potential-energy surfaces (PESs). Our test sets include the extensive S22x5 and S66x8 data sets. Our results indicate that subsystem DFT PESs strongly vary depending on the functional. LDA results are usually quite good, but behave differently from their KS counterparts. GGA results from the popular Perdew–Wang (PW91) set of functionals produce PESs that are often, but not in general overbinding. Results from Becke–Perdew (BP86) GGAs, by contrast, show the typical problems known from the corresponding KS results. We provide some preliminary results for empirical corrections for both PW91 and BP86 in subsystem DFT.

Graphical abstract: Subsystem-DFT potential-energy curves for weakly interacting systems

Back to tab navigation

Supplementary files

Article information


Submitted
28 Oct 2014
Accepted
27 Nov 2014
First published
23 Dec 2014

This article is Open Access

Phys. Chem. Chem. Phys., 2015,17, 14323-14341
Article type
Paper

Subsystem-DFT potential-energy curves for weakly interacting systems

D. Schlüns, K. Klahr, C. Mück-Lichtenfeld, L. Visscher and J. Neugebauer, Phys. Chem. Chem. Phys., 2015, 17, 14323
DOI: 10.1039/C4CP04936E

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. Material from this article can be used in other publications provided that the correct acknowledgement is given with the reproduced material.

Reproduced material should be attributed as follows:

  • For reproduction of material from NJC:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the Centre National de la Recherche Scientifique (CNRS) and the RSC.
  • For reproduction of material from PCCP:
    [Original citation] - Published by the PCCP Owner Societies.
  • For reproduction of material from PPS:
    [Original citation] - Published by The Royal Society of Chemistry (RSC) on behalf of the European Society for Photobiology, the European Photochemistry Association, and RSC.
  • For reproduction of material from all other RSC journals:
    [Original citation] - Published by The Royal Society of Chemistry.

Information about reproducing material from RSC articles with different licences is available on our Permission Requests page.


Social activity

Search articles by author

Spotlight

Advertisements