Abstract
The exquisite features of molecular photochemistry are key to any complete understanding of the chemical processes governed by potential energy surfaces (PESs). It is well established that multiple dissociation pathways relate to nonadiabatic transitions between multiple coupled PESs. However, little detail is known about how the single PES determines reaction outcomes. Here we perform detailed experiments on HNCO photodissociation, acquiring the state-specific correlations of the NH (a(1)Δ) and CO (X(1)Σ(+)) products. The experiments reveal a trimodal CO rotational distribution. Dynamics simulations based on a full-dimensional machine-learning-based PES of HNCO unveil three dissociation pathways exclusively occurring on the S(1) excited electronic state. One pathway, following the minimum energy path (MEP) via the transition state, contributes to mild rotational excitation in CO, while the other two pathways deviating substantially from the MEP account for relatively cold and hot CO rotational state populations. These peculiar dynamics are unambiguously governed by the S(1) state PES topography, i.e., a narrow acceptance cone in the vicinity of the transition state region. The dynamical picture shown in this work will serve as a textbook example illustrating the importance of the PES topography in molecular photochemistry.