| Abstract
| - The photodissociations of two metal nitrosyl compounds, Co(CO)3NO and Mn(CO)4NO, were studied at 450nm, in the metal-to-nitrosyl charge-transfer region for both compounds. The rotational distributions of freeNO in the v‘ ‘ = 0 vibrational state were determined by laser-induced fluorescence excitation. A SurprisalAnalysis shows that the NO population distributions display a dynamical bias toward lower rotation in bothcompounds. The similarity between the NO rotational distributions is surprising, considering that Co(CO)3NOwas expected to dissociate through a bent transition state and Mn(CO)4NO was not. The spin−orbit populationsof the NO products (2Π1/2 and 2Π3/2) are equally populated in both compounds, indicating that the electronicsurfaces that produce these two states are strongly coupled at the transition state. An upper limit of the M−NObond dissociation energy is estimated at 52 kcal/mol from the rotational assignments.
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