Insights into the Mechanism of Nonadiabatic Photodissociation from Product Vibrational Distributions. The Remarkable Case of Phenol.

The fate of a photoexcited molecule is often strongly influenced by electronic degeneracies, such as conical intersections, which break the Born-Oppenheimer separation of electronic and nuclear motion. Detailed information concerning internal energy redistribution in a nonadiabatic process can be extracted from the product state distribution of a photofragment in photodissociation. Here, we focus on the nonadiabatic photodissociation of phenol and discuss the internal excitation of the phenoxyl fragment using both symmetry analysis and wave packet dynamics. It is shown that unique and general selection rules exist, which can be attributed to the geometric phase in the adiabatic representation. Further, our results provide a reinterpretation of the experimental data, shedding light on the impact of conical intersections on the product state distribution.