Photodissociation of the group VIB (Cr,Mo,W) hexacarbonyls has been studied at 248 nm using molecular beam photofragment spectroscopy. One, two and three photon processes have been observed. Analysis of the product velocity distributions shows that the photodissociation mechanism consists of sequential CO eliminations with the nth photon channel best described as the single photon photodissociation of the stable products of the n-1st photon channel. The product translational energy distribution for the first CO elimination step is quantitatively similar for all three hexacarbonyls and characteristic of a repulsive translational energy release. The product translational energy distributions of all subsequent CO elimination steps are accurately described by a simple, microcanonical model. Qualitative molecular orbital considerations suggest that the large product translational energy observed in the first CO elimination step results from a repulsive σ interaction between the closed shell CO ligand and an excited molecular orbital which has a significant admixture of metal (n+1)pz, (n+1)s and ndz2 orbitals. This repulsive interaction is absent in the remaining CO elimination steps because there are vacancies in the coordination shell along the z axis.
Water clusters formed in a molecular beam are predissociated by tunable, pulsed, infrared radiation in the frequency range ~1 2900~3750 em . The recoiling fragments are detected off axis from the molecular beam using a rotatable mass spectrometer. Arguments are presented which show that the measured frequency dependent signal at a fixed detector angle is proportional to the absorption spectrum of the clusters. It is found that the spectra of clusters containing three or more water molecules are remarkably similar to the liquid phase spectrum.Dynamical information on the predissociation process is obtained from the velocity distribution of the fragments.
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