Collect. Czech. Chem. Commun. 2003, 68, 489-508

A Comprehensive Computational Study on OCH+-Rg (Rg = He, Ne, Ar, Kr, Xe) Complexes

Yinghong Sheng and Jerzy Leszczynski*

The Computational Center for Molecular Structure and Interactions, Department of Chemistry, Jackson State University, P. O. Box 17910, 1400 J. R. Lynch Street, Jackson, MS 39217, U.S.A.


The equilibrium geometries, harmonic vibrational frenquencies, and the dissociation energies of the OCH+-Rg (Rg = He, Ne, Ar, Kr, and Xe) complexes were calculated at the DFT, MP2, MP4, CCSD, and CCSD(T) levels of theory. In the lighter OCH+-Rg (Rg = He, Ne, Ar) rare gas complexes, the DFT and MP4 methods tend to produce longer Rg-H+ distance than the CCSD(T) level value, and the CCSD-calculated Rg-H+ bond lengths are slightly shorter. DFT method is not reliable to study weak interaction in the OCH+-He and OCH+-Ne complexes. A qualitative result can be obtained for OCH+-Ar complex by using the DFT method; however, a higher-level method using a larger basis set is required for the quantitative predictions. For heavier atom (Kr, Xe)-containing complexes, only the CCSD method predicted longer Rg-H+ distance than that obtained at the CCSD(T) level. The DFT method can be applied to obtain the semiquantitative results. The relativistic effects are expected to have minor effect on the geometrical parameters, the H+-C stretching mode, and the dissociation energy. However, the dissociation energies are sensitive to the quality of the basis set. The nature of interaction between the OCH+ ion and Rg atoms was also analyzed in terms of the interaction energy components.

Keywords: Rare gases complexes; Weak interaction; Harmonic vibrational frequency; Dissociation energy; Energy decomposition; Ab initio calculations; MP2; DFT; CCSD.

References: 55 live references.