An ab initio intermolecular potential energy surface for the F(2) dimer.
Two analytical representations for the potential energy surface of the F(2) dimer were constructed on the basis of ab initio calculations up to the fourth-order of Møller-Plesset (MP) perturbation theory. The best estimate of the complete basis set limit of interaction energy was derived for analysis of basis set incompleteness errors. At the MP4/aug-cc-pVTZ level of theory, the most stable structure of the dimer was obtained at R = 6.82 au, theta(a) = 12.9 degrees , theta(b) = 76.0 degrees , and phi = 180 degrees , with a well depth of 716 microE(h). Two other minima were found for canted and X-shaped configurations with potential energies around -596 and -629 microE(h), respectively. Hexadecapole moments of monomers play an important role in the anisotropy of interaction energy that is highly R-dependent at intermediate intermolecular distances. The quality of potentials was tested by computing values of the second virial coefficient. The fitted MP4 potential has a more reasonable agreement with experimental values.
Karimi-Jafari
Mohammad H
MH
Department of Physical Chemistry, School of Chemistry, University of Tehran, Tehran, Iran.
Maghari
Ali
A