INFRARED-SPECTRA OF BERYLLIUM CARBONYLS FROM REACTIONS OF BERYLLIUM ATOMS WITH CARBON-MONOXIDE IN SOLID ARGON

Pulsed laser evaporated beryllium atoms have been reacted with Ar:CO gaseous mixtures during condensation onto a 10 K substrate. Identification of several novel beryllium carbonyls is made on the basis of further reactions on sample warming to 30 K, changes in relative Be/CO concentration, (CO)-C-13 and (CO)-O-18 isotopic substitution, and ab initio calculations at the SCF level using the 6-311G* basis sets. Although the tripler BeCO molecule has weak bonding character, it is less stable than Be + CO and cannot be formed on annealing in solid argon. The primary product infrared bands from the reaction of Be + CO during condensation are identified as BeBeCO and OCBeBeCO, which are decreased on broadband photolysis and also reproduced on annealing the matrix. Secondary product bands due to higher carbonyls grow strongly on annealing and are identified as the stable Be(CO)(2), Be(CO)(3), BeBe(CO)(2), (OC)BeBe(CO)(2), and (OC)(2)BeBe(CO)(2) molecules. The former four new beryllium carbonyls are characterized by Be-C as well as C-O stretching fundamentals. It is clear that clustering of Be atoms and CO molecules leads to product formation in these experiments.