Ab initioand DFT studies on van der Waals trimers: The OCS · (CO2)2complexes

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Abstract
Ab initio calculations [MP2, MP4SDTQ, and QCISD(T)] using different basis sets [6‐31G(d,p), cc‐pVXZ (X = D, T, Q), and aug‐cc‐pVDZ] and density functional theory [B3LYP/6‐31G(d,p)] calculations were carried out to study the OCS · (CO2)2 van der Waals trimer. The DFT has proved inappropriate to the study of this type of systems where the dispersion forces are expected to play a relevant role. Three minima isomers (two noncyclic and one cyclic) were located and characterized. The most stable isomer exhibits a noncyclic barrel‐like structure whose bond lengths, angles, rotational constants, and dipole moment agree quite well with the corresponding experimental values of the only structure observed in recent microwave spectroscopic studies. The energetic proximity of the three isomers, with stabilization energies of 1442, 1371, and 1307 cm−1, respectively, at the CBS‐MP2/cc‐pVXZ (X = D, T, Q) level, strongly suggests that the two unobserved structures should also be detected as in the case of the (CO2)3 trimer where both noncyclic and cyclic isomers have been reported to exist. The many‐body symmetry‐adapted perturbation theory is employed to analyze the nature of the interactions leading to the formation of the different structures. The three‐body contributions are small and stabilizing for the two most stable structures and almost negligible for the cyclic isomer. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 444–455, 2002; DOI 10.1002/jcc.10041
Funding Information
  • DGES (PB97-0399-C03-03)

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