Infrared studies of matrix isolated sodium and potassium chloride and cyanide dimers

The infrared spectra of matrix isolated sodium and potassium chlorides and cyanides in different inert gas matrices were examined over the range 4000 cm^?1 to 33 cm^?1. A study of the effect of superheating the vapor species on the spectra has been carried out. Temperature cycling experiments have been pursued in an attempt to differentiate between bands due to monomers, dimers, and higher polymers. Isotopic frequency shifts were measured for a carbon-13 enriched sample of sodium cyanide and carbon-13 and nitrogen-15 enriched samples of potassium cyanide in the CN region. Symmetry force constants were calculated assuming a cyclic rhombic structure for the dimers. In the case of the cyanide dimer, the CN group of the molecule was considered as a halide atom. Finally a comparison is given between the symmetry force constants of the dimers of the alkali metal fluorides, cyanides and chlorides.