Intermolecular interactions of nitrobenzene-benzene complex and nitrobenzene dimer: significant stabilization of slipped-parallel orientation by dispersion interaction

The CCSD(T) level interaction energies of eight orientations of nitrobenzene-benzene complexes and nine orientations of nitrobenzene dimers at the basis set limit have been estimated. The calculated interaction energy of the most stable slipped-parallel (C(s)) nitrobenzene-benzene complex was -4.51 kcal/mol. That of the most stable slipped-parallel (antiparallel) (C(2h)) nitrobenzene dimer was -6.81 kcal/mol. The interaction energies of these complexes are significantly larger than that of the benzene dimer. The T-shaped complexes are substantially less stable. Although nitrobenzene has a polar nitro group, electrostatic interaction is always considerably weaker than the dispersion interaction. The dispersion interaction in these complexes is larger than that in the benzene dimer, which is the cause of the preference of the slipped-parallel orientation in these complexes.