Theoretical characterization of structures and energies of benzene-(H2S)n and (H2S)n (n=1-4) clusters -: art. no. 204315

An ab initio study was performed in clusters up to four H-2(2)2(2)2(2)n(S molecules and benzene using calculations at MP2/6-31+G* and MP2/aug-cc-pVDZ levels. Differences between both sets of calculations show the importance of using large basis sets to describe the intermolecular interactions in this system. The obtained binding energies reflect that benzene has not the same behavior in H)S as in water, pointing to a higher solubility of this molecule in H(S than in water. The Bz-cluster binding energy was fitted to an asymptotic representation with a maximum value of the energy of -8.00 kcal/mol that converges in a cluster with 12 H)S molecules. The obtained intermolecular distance in the Bz-H(S dimer is similar to the experimental value; however, the difference is much larger for the angles defining the orientation. The influence of benzene produces a distortion of the (H)S) (clusters, so the intermolecular distances change with regard to the (H)(S))(2)(n) S-isolated clusters. Frequency shifts are larger in clusters with benzene than without it. In the smallest clusters the shift associated to the stretching of the S-H bonded to benzene is the largest one, but for the cluster with three H(2) molecules this stretching is combined with the other S-H stretching of the molecule so the resulting shift is not the largest one.