Infrared spectroscopic and density functional theory studies on the reactions of cadmium atoms with carbon monoxide...

Reactions of laser-ablated cadmium atoms with carbon monoxide molecules in solid argon have been investigated using matrix isolation infrared spectroscopy. On the basis of isotopic substitution, the absorption at 1858.2 cm(-1) is assigned to the C-O stretching of the CdCO molecule, which is formed during the sample deposition. Cadmium di- and tricarbonyls, Cd(CO)n (n = 2, 3), have not been observed under the same experimental conditions. Density functional theory calculations have been performed on the cadmium carbonyls Cd(CO)n (n = 1-3), which lend strong support to the experimental assignments of the infrared spectra. It is predicted that the CdCO molecule is a linear triplet molecule and its formation involves Cd 5s --> 5p promotion. This promotion increases the Cd-CO bonding by decreasing the sigma repulsion and increasing the Cd 5p orbital --> CO pi back-donation. The absence of cadmium di- and tricarbonyls, Cd(CO)n (n = 2, 3), has also been discussed in some detail.