Reactions of Laser-Ablated Zinc and Cadmium Atoms with CO: Infrared Spectra of the Zn(CO)x (x = 1−3), CdCO-, and Cd(CO)2 Molecules in Solid Neon

Abstract

Reactions of laser-ablated zinc and cadmium atoms with carbon monoxide molecules in solid neon have been investigated using matrix-isolation infrared spectroscopy. Based on the isotopic substitution, absorptions at 1852.2, 1901.9, 1945.9, and 1995.2 cm(-1) are assigned to the C-O stretching vibrations of the ZnCO, Zn(CO)(2), and Zn(CO)(3) molecules. Absorptions at 1735.8, 1961.3, and 2035.7 cm(-1) are assigned to the C-O stretching vibrations of the CdCO(-) and Cd(CO)(2) molecules. In contrast with the previous argon experiments, more species and more valuable information about the reaction of zinc and cadmium atoms with CO have been obtained in solid neon. Density functional theory calculations have been performed on these zinc and cadmium carbonyls. The agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts substantiates the identification of these carbonyls from the matrix infrared spectrum. The present experiments also reveal that zinc is more reactive with CO than cadmium.