Interaction energies computed with density functional theory can be divided into physically meaningful components by symmetry-adapted perturbation theory (DFT-SAPT) or the canonical energy decomposition analysis (EDA). In this work, the decomposition results obtained by these schemes were compared for more than 200 hydrogen-, halogen-, and pnicogen-bonded, dispersion-bound, and mixed complexes to investigate their similarity in the evaluation of the nature of noncovalent interactions. BLYP functional with D3(BJ) correction was used for the EDA scheme, whereas asymptotically corrected PBE0 functional for DFT-SAPT provided some of the best combinations for description of noncovalent interactions. Both schemes provide similar results concerning total interaction energies and insight into the individual energy components. For most complexes, the dominant energetic term was identified equally by both decomposition schemes. Because the canonical EDA is computationally less demanding than the DFT-SAPT, the former can be especially used in cases where the systems investigated are very large.

Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling VU Amsterdam De Boelelaan 1083 1081 HV Amsterdam The Netherlands

Institute of Organic Chemistry and Biochemistry Academy of Sciences of the Czech Republic 166 10 Prague 6 Czech Republic

Leiden Institute of Chemistry Gorlaeus Laboratories Leiden University P O Box 9502 2300 RA Leiden The Netherlands

Regional Centre of Advanced Technologies and Materials Department of Physical Chemistry Palacký University 771 46 Olomouc Czech Republic

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