On the role of higher-order correlation effects on the induction interactions between closed-shell molecules.
High-order correlation contributions to the second-order induction energy were studied for various representative van der Waals complexes. It was found that the induction energy obtained by the truncation of the relaxed Møller-Plesset expansion in the second or third order is in most cases quite close to the induction energy computed with the coupled-cluster method (restricted to single and double excitations). Also, the effect of triples excitations on this perturbation term is usually small. However, given an oscillatory behaviour of the Møller-Plesset induction corrections, the coupled-cluster method seems to be better suited to a reliable calculation of the induction energy. The sources of the remaining differences between the interaction energies computed by symmetry-adapted perturbation theory and those computed by the supermolecule coupled-cluster method (restricted to single, double, and noniterative triple excitations) are examined. It has been found that they can be attributed to the higher-order correlation terms in the second-order dispersion and exchange-induction corrections.
Korona
Tatiana
T
Faculty of Chemistry, University of Warsaw, Pasteura 1, 02-093, Warsaw, Poland. tania@chem.uw.edu.pl
D000465:Algorithms; D003198:Computer Simulation; D004583:Electrons; D004735:Energy Transfer; D007700:Kinetics; D008958:Models, Molecular; D011789:Quantum Theory; D013816:Thermodynamics