Interaction of rare-gas-containing molecules with nitrogen:: Matrix-isolation and ab initio study of HArF•••N2, HKrF•••N2, and HKrCl•••N2 complexes

The complexes of HArF, HKrF, and HKrCl with nitrogen molecules have been studied computationally and experimentally. With the help of computations the experimental data can be interpreted as showing the presence of two complex configurations, one linear and one bent. Vibrational properties of the studied molecules are very sensitive to the intermolecular interactions and complexation induces an exceptionally large blueshift (>100 cm(-1) for HKrCl) to the H-Ar and H-Kr stretching frequency, especially for the linear configurations. The interaction energies without zero-point energy correction are between 400 and 800 cm(-1). According to the energy decomposition scheme, the electrostatic forces provide the most important interaction in the linear complex configurations. For the bent complexes, electrostatic and dispersion forces are competing as a leading attractive interaction. (C) 2003 American Institute of Physics.