화학공학소재연구정보센터
Journal of Chemical Physics, Vol.104, No.17, 6569-6576, 1996
Ab-Initio Study of Van-der-Waals Interaction of CO2 with Ar
The ab initio potential energy surface of the ArCO2 cluster is calculated using the supermolecular Moller-Plesset perturbation theory (S-MPPT) and dissected into its fundamental components; electrostatic, exchange, induction, and dispersion energies. The surface contains a single minimum for the perpendicular approach of Ar toward the C atom which has a well depth of similar to 210 cm(-1) at R=6.5 a(0). This value is obtained using an extended basis set supplied with the bond functions and the fourth order supermolecular Moller-Plesset calculations, and is expected to be accurate to within +/-5%. The areas of the surface corresponding to the collinear approach of Ar to CO2 contain an extended plateau. The saddle point in this region for R=9.0 a(0) is stabilized by 117 cm(-1). The analytical pair potential for Ar-CO2 obtained by fitting to the individual interaction components is provided. The three-body effects in the related cluster, Ar2CO2, are examined for two configurations of the Ar2CO2 cluster. The overall nonadditivity is dominated by the three-body dispersion effect; however, the exchange nonadditivity is the most anisotropic. The sources of this anisotropy are discussed.