Vector Correlations in the 225 nm Photodissociation of Co(CO)₃NO

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Metal nitrosyls are fascinating compounds because they undergo significant geometry changes in the excited state. The volatile compound, Co(CO)₃NO, is a model for understanding the excited-state behavior. In this experiment, Co(CO)₃NO was photodissociated in a DC-sliced velocity mapping ion imaging apparatus with 1 + 1′ resonance-enhanced multiphoton ionization (REMPI) detection of the nascent NO. Ion images were collected for different linear polarization of the dissociation and probe lasers to determine the vector correlations in the photodissociation. The fastest NO products arise from an excitation parallel to the dissociating Co-NO bond. The Co-NO bond bends in the excited state, producing an NO photoproduct with angular momentum that is also aligned in the laboratory frame. The μ-v-J vector correlations were measured and are consistent with the orientation μ||v⊥J caused by an excited-state Co-NO bend prior to dissociation. Slower NO photoproducts emerge with smaller vector correlations stemming from fragmentation, parent or fragment rotation, or intersystem crossing.