Molecular structure and infrared spectra of (HXeCN)n (n=2, 3 or 4)

The structure, energetics, and vibrational spectra of the (HXeCN)2 dimer were investigated at the CCSD(T), MP2 and B3LYP levels. Such properties of the (HXeCN)3 trimer and (HXeCN)4 tetramer were investigated at the B3LYP level. The dimer, trimer, and tetramer were predicted to have a C2h, C2v, and D2d structure, respectively. In all of these oligomers, the N⋯Xe intermonomeric interaction is the most important one for holding the monomers together. Included with the ZPVE and BSSE, the stabilization energy of the dimer is 12.36 kcal/mol at the CCSD(T) level, while those of the dimer, trimer, and tetramer are 10.42, 18.23, and 31.34 kcal/mol, respectively, at the B3LYP level. At the B3LYP level, with respect to those of the isolated monomer, the C-Xe and Xe-H asymmetric stretching frequencies are shifted by -11.2 and +128.0 cm(-1) for the dimer, -51.6, +220.7 and -11.5, +96.6 cm(-1) for the trimer, and -14.1 and +201.8 cm(-1) for the tetramer.