| Abstract
| - Reactions of laser-ablated cadmium atoms with carbon monoxide molecules in solid argon have beeninvestigated using matrix isolation infrared spectroscopy. On the basis of isotopic substitution, the absorptionat 1858.2 cm-1 is assigned to the C−O stretching of the CdCO molecule, which is formed during the sampledeposition. Cadmium di- and tricarbonyls, Cd(CO)n (n = 2, 3), have not been observed under the sameexperimental conditions. Density functional theory calculations have been performed on the cadmium carbonylsCd(CO)n (n = 1−3), which lend strong support to the experimental assignments of the infrared spectra. It ispredicted 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 σ repulsion and increasing the Cd 5p orbital→ CO π* back-donation. The absence of cadmium di- and tricarbonyls, Cd(CO)n (n = 2, 3), has also beendiscussed in some detail.
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