The interaction of Ar with H2 and HCl has been studied using Møller-Plesset perturbation theory (MP2, MP3, MP4) and coupled-cluster [CCSD, CCSD(T)] methods with augmented correlation consistent basis sets. Basis sets as large as triply augmented quadruple zeta quality were used to investigate the convergence trends. Interaction energies were determined using the supermolecule approach with the counterpoise correction to account for basis set superposition error. Comparison with the available empirical potentials finds excellent agreement for both binding energies and transition state. For Ar-H2, the estimated complete basis set (CBS) limits for the binding energies of the two equivalent minima and the connecting transition state (TS) are, respectively, 55 and 47cm-1 at the MP4 level and 54 and 46cm-1 at the CCSD(T) level, respectively [the XC(fit) empirical potential of Bissonnette et al. [J. Chem. Phys. 105, 2639 (1996)] yields 56.6 and 47.8cm-1 for H2 (v=0)]. The estimated CBS limits for the binding energies of the two minima and transition state of Ar-HCl are 185, 155, and 109cm-1 at the MP4 level and 176, 147, and 105cm-1 at the CCSD(T) level, respectively [the H6(4,3,0) empirical potential of Hutson [J. Phys. Chem. 96, 4237 (1992)] yields 176.0, 148.3, and 103.3cm-1 for HCl (v=0)]. Basis sets containing diffuse functions of (dfg) symmetries were found to be essential for accurately modeling these two complexes, which are largely bound by dispersion and induction forces. Highly correlated wave functions were also required for accurate results. This was found to be particularly true for ArHCl, where significant differences in calculated binding energies were observed between MP2, MP4, and CCSD(T).
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry