Benchmark Calculations of Three-Body Intermolecular Interactions and the Performance of Low-Cost Electronic Structure Methods

0446669 - ÚOCHB 2016 RIV US eng J - Článek v odborném periodiku
Řezáč, Jan - Huang, Y. - Hobza, Pavel - Beran, G. J. O.
Benchmark Calculations of Three-Body Intermolecular Interactions and the Performance of Low-Cost Electronic Structure Methods.
Journal of Chemical Theory and Computation. Roč. 11, č. 7 (2015), s. 3065-3079. ISSN 1549-9618. E-ISSN 1549-9626
Grant CEP: GA ČR GP13-01214P; GA ČR GBP208/12/G016
Institucionální podpora: RVO:61388963
Klíčová slova: density functional theory * Plesset perturbation theory * noncovalent interactions * interaction energies
Kód oboru RIV: CF - Fyzikální chemie a teoretická chemie
Impakt faktor: 5.301, rok: 2015

Many-body noncovalent interactions are increasingly important in large and/or condensed-phase systems, but the current understanding of how well various models predict these interactions is limited. Here, benchmark complete-basis set coupled cluster singles, doubles, and perturbative triples (CCSD(T)) calculations have been performed to generate a new test set for three-body intermolecular interactions. This "3B-69" benchmark set includes three-body interaction energies for 69 total trimer structures, consisting of three structures from each of 23 different molecular crystals. By including structures that exhibit a variety of intermolecular interactions and packing arrangements, this set provides a stringent test for the ability of electronic structure methods to describe the correct physics involved in the interactions. Both MP2.5 (the average of second- and third-order Moller Plesset perturbation theory) and spin-componentscaled CCSD for noncovalent interactions (SCS-MI-CCSD) perform well. MP2 handles the polarization aspects reasonably well, but it omits three-body dispersion. In contrast, many widely used density functionals corrected with three-body D3 dispersion correction perform comparatively poorly. The primary difficulty stems from the treatment of exchange and polarization in the functionals rather than from the dispersion correction, though the three-body dispersion may also be moderately underestimated by the D3 correction.
Trvalý link: http://hdl.handle.net/11104/0248664