Theoretical study of the complexes of dichlorobenzene isomers with argon. I. Global potential energy surface for all the isomers with application to intermolecular vibrations.

Abstract

The complexes of para- (p-), meta- (m-), and ortho- (o-)dichlorobenzene (DCB) isomers with argon are studied using an ab initio method. The interaction energy in the ground electronic state of the complexes has been calculated using the CCSD(T) method (coupled cluster method including single and double excitations with perturbative triple excitations) and Dunning's double-ζ (aug-cc-pVDZ) basis set supplemented by midbond functions. Local interaction parameters have been defined and interesting relations fulfilled by them, independent of the DCB isomer, have been revealed. This finding has allowed us to construct the accurate global analytical intermolecular potential energy surface for all the DCB-Ar complexes with the same set of parameters, except for the monomer geometries. Each complex is characterized by two symmetrically equivalent global minima, one located above and the other located below the monomer plane at distances equal to 3.497 Å, 3.494 Å, and 3.485 Å for p-, m-, and o-isomers of DCB bound to Ar, respectively. Additionally, the Ar atom is shifted from the geometrical center of the DCB monomer towards the chlorine atoms by the value xe of 0.182 Å for m-isomer and 0.458 Å for o-isomer. The calculated binding energy De of 460 cm-1, 465 cm-1, and 478 cm-1 for p-, m-, and o-complex, respectively, are related to xe by simple relations. The intermolecular bending fundamentals calculated from PES depend strongly on the isomer structure. The calculated dissociation energies fit in the intervals estimated by the experiment of Gaber et al. for the S0 state [Phys. Chem. Chem. Phys. 11, 1628 (2009)].