A computational study of the hydrogen-bonded complexes FArH⋯OCO and FKrH⋯OCO

Linear hydrogen-bonded complexes of carbon dioxide with the rare-gas compounds HArF and HKrF were found to be stable at the MP2/6-311++G(2d,2p) level of theory. The FArH⋯OCO and FKrH⋯OCO complexes have zero-point energy corrected binding energies of 13 and 8 kJ mol−1, respectively. Large blue shifts of the Rg–H harmonic stretching frequency and red shifts of the F–Rg stretch were obtained for both complexes. The electron density rearrangement on complexation was also examined. A perturbation theory model of frequency shifts was found to be in good agreement with the ab initio results.