The information contained in magnetic-state-selected photodissociation differential cross sections is examined by means of a quantum mechanical time-independent theory. Motivated by recent experimental demonstration of the possibility to select molecules with respect to their magnetic-rovibronic state and measure the energy-resolved angular distribution following their photofragmentation, we examine analytically and numerically the sensitivity of such angular distributions to the structure and the dynamics of the studied system. It is found that magnetic-state-selected cross sections contain significant information with respect to both the electronic structure (the potential energy surfaces as well as the transition dipole vector) and the reaction dynamics of photoinitiated reactions, which cannot be obtained from more averaged observable. In particular we find that such cross sections provide a mapping of the transition dipole vector which couples the ground state with the excited manifold. This feature is traced to the coherent excitation of a small subset of helicity states in the absorption process. It is suggested that the information contained in these angular distributions can be appreciated and extracted by preceding the experimental measurements with theoretical analysis.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry