Trends in the Optical Signatures for Transition-Metal Oxide Carbonyl Complexes. Evaluation of Transition-Metal Carbonyl, M(CO)x, Binding Energies

Article abstract of DOI:10.1021/ja00224a007

Transition-metal atoms entrained in argon, helium, and CO are oxidized with ozone (O3) and nitrogen dioxide (NO2) to study the nature of the metal atom complexation with CO.We establish a method for evaluating M-CO binding energies through comparison of the chemiluminescent emission from the oxidation of argon- and CO-entrained transition-metal atoms.These studies have thus far yielded E_binding(Ti(CO)x) ca. 1.75 eV and E_binding(NiCO) ca. 1.10 eV, the latter in excellent agreement with previous experimental and theoretical evaluations of the Ni-CO bond energy.We identify the optical signatures for transition-metal oxide carbonyl (MOCO) complexes formed in the oxidation of M(CO) complexes.We outline trends in the nature of the observed metal oxide complex emissions.The current study suggests a method for obtaining the spectra of transition-metal carbonyl (M(CO)x, x=1,2) complexes.