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

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 mu-v-J vector correlations were measured and are consistent with the orientation mu||v perpendicular to 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.

Automated summary

Metal nitrosyls are interesting due to their significant geometrical changes in the excited state. Co(CO)3NO is a volatile compound used as a model to study excited-state behavior. In this experiment, Co(CO)3NO was photodissociated and ion images were collected to determine the vector correlations in the photodissociation. The results showed that the fastest NO products came from an excitation parallel to the dissociating Co-NO bond.