Abstract
The bond dissociation energy of Co + 2 has been measured by the onset of predissociation in a dense electronic spectrum by the detection of the fragment Co + ion. The value obtained, D 0 0(Co + 2) = 2.765±0.001 eV, compares well to the previously accepted value of 2.75±0.10 eV, obtained using collision-induced dissociation (CID) methods. This represents the first accurate determination of the bond strength of a transition metal cluster cation by photodissociation. The agreement between the photodissociation and CID measurements suggests that predissociation of open d-subshell transition metal clusters with a sufficient density of electronic states sets in quite abruptly at the thermodynamic threshold. Criteria for the validity of the assignment of a predissociation threshold as the thermochemical bond strength are discussed, using Co + 2 and other molecules as examples.
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