Intermolecular potential energy surface for CS2 dimer

Hossein Farrokhpour, Zainab Mombeini, Mansoor Namazian, Michelle L. Coote

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14 Citations (Scopus)

Abstract

A new four-dimensional intermolecular potential energy surface for CS 2 dimer is obtained by ab initio calculation of the interaction energies for a range of configurations and center-of-mass separation distances for the first time. The calculations were performed using the supermolecular approach at the MØller-Plesset second-order perturbation (MP2) level of theory with the augmented correlation consistent basis sets (aug-cc-pVxZ, x = D, T) and corrected for the basis-set superposition error using the full counterpoise correction method. A two-point extrapolation method was used to extrapolate the calculated energy points to the complete basis set limit. The effect of using the higher levels of theory, quadratic configuration interaction containing single, double, and perturbative triple excitations QCISD(T) and coupled cluster singles, doubles and perturbative triples excitations CCSD(T), on the shape of potential energy surface was investigated. It is shown that the MP2 level of theory apparently performs extremely poorly for describing the intermolecular potential energy surface, overestimating the total energy by a factor of nearly 1.73 in comparison with the QCISD(T) and CCSD(T) values. The value of isotropic dipole-dipole dispersion coefficient (C6) of CS2 fluid was obtained from the extrapolated MP2 potential energy surface. The MP2 extrapolated energy points were fitted to well-known analytical potential functions using two different methods to represent the potential energy surface analytically. The most stable configuration of the dimer was determined at R = 6.23 au, α = 90°, β = 90°, and δ = 90°, with a well depth of 3.980 kcal mol-1 at the MP2 level of theory. Finally, the calculated second virial coefficients were compared with experimental values to test the quality of the presented potential energy surface.

Original languageEnglish
Pages (from-to)797-809
Number of pages13
JournalJournal of Computational Chemistry
Volume32
Issue number5
DOIs
Publication statusPublished - 15 Apr 2011
Externally publishedYes

Keywords

  • basis-set superposition error
  • CCSD(T)
  • CS dimer
  • extrapolation
  • isotropic dipole-dipole dispersion coefficient
  • MØller-Plesset second-order perturbation (MP2)
  • potential energy surface
  • QCISD(T)
  • theory

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