Theoretical study of the complexes of dichlorobenzene isomers with argon. II. SAPT analysis of the intermolecular interaction

Abstract

The interaction of argon with dichlorobenzene isomers (DCB-Ar) has been analyzed with the help of the symmetry-adapted perturbation theory based on the density functional description of monomer properties (DFT-SAPT). The global potential energy surface (PES) of these complexes determined from the DFT-SAPT interaction energy (Eint) values has been compared to the CCSD(T) (coupled cluster method including single and double excitations with perturbative triple excitations) PES reported in the companion Paper I [J. Makarewicz and L. Shirkov, J. Chem. Phys. 150, 074301 (2019)]. The equilibrium structures and the binding energies found using DFT-SAPT and CCSD(T) methods combined with adequate basis sets are in good agreement. Besides DCB-Ar, we confirmed that DFT-SAPT gives accurate values of these quantities for other complexes containing an aromatic molecule and Ar. However, DFT-SAPT PES of DCB-Ar is flatter than the corresponding CCSD(T) one. As a result, the intermolecular vibrational energies are systematically underestimated. The analytical form of the important interrelations between SAPT components of Eint, established previously by us [J. Makarewicz and L. Shirkov, J. Chem. Phys. 144, 204115 (2016)], has been approved for the DCB-Ar complexes. Simplified SAPT models based on these relations have been employed to explain physical reasons for differences in the structures and the binding energies of DCB-Ar isomers. It is shown that the equilibrium distance of Ar to DCB plane and the binding energy are determined mainly by dispersion energy. The shift of Ar toward Cl is caused by both exchange and dispersion terms.