Ab initio potential energy surface and predicted microwave spectra for ArOCS dimer and structures of ArnOCS (n = 2–14) clusters

An ab initio potential energy surface for the Ar‐OCS dimer was calculated using the coupled‐cluster singles and doubles with noniterative inclusion of connected triples [CCSD(T)] with a large basis set containing bond functions. The interaction energies were obtained by the supermolecular approach with the full counterpoise correction for the basis set superposition error. The CCSD(T) potential was found to have two minima corresponding to the T‐shaped and the collinear ArSCO structures. The two‐dimensional discrete variable representation method was employed to calculate the rovibrational energy levels for five isotopomers ArOCS, ArOC34S, ArO13CS, Ar18OCS, and Ar17OCS. The calculated pure rotational transition frequencies for the vibrational ground state of the five isotopomers are in good agreement with the observed values. The corresponding microwave spectra show that the b‐type transitions (Δ Ka = ±1) are significantly stronger than the a‐type transitions (Δ Ka = 0). Minimum‐energy structures of the Ar2OCS trimer were been determined with MP2 optimization, whereas the minimum‐energy structures of the ArnOCS clusters with n = 3–14 were obtained with the pairwise additive potentials. It was found that there are two minima corresponding to one distorted tetrahedral structure and one planar structure for the ternary complex. The 14 nearest neighbor Ar atoms form the first solvation shell around the OCS molecule. © 2006 Wiley Periodicals, Inc. J Comput Chem 27: 1045–1053, 2006

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