Infrared Spectroscopic and Density Functional Theory Study on the Reactions of Rhodium and Cobalt Atoms with Carbon Dioxide in Rare-Gas Matrixes

Abstract

Reactions of laser-ablated rhodium and cobalt atoms with carbon dioxide molecules in solid argon and neon have been investigated using matrix isolation infrared spectroscopy. The OMCO, O2MCO, OMCO(-) (M = Rh, Co), OCo2CO, and OCoCO(+) molecules have been formed and characterized on the basis of isotopic shifts, mixed isotopic splitting patterns, ultraviolet irradiation, CCl4-doping experiments, and the change of laser power. Density functional theory calculations have been performed on these products. The overall agreement between the experimental and calculated vibrational frequencies, relative absorption intensities, and isotopic shifts supports the identification of these products from the matrix infrared spectrum.