UC Berkeley

Conical intersections between electronic states often dictate the chemistry of photoexcited molecules. Recently developed sources of ultrashort extreme ultraviolet (XUV) pulses tuned to element-specific transitions in molecules allow for the unambiguous detection of electronic state-switching at a conical intersection. Here, the fragmentation of photoexcited iso-propyl iodide and tert-butyl iodide molecules (i-C₃H₇I and t-C₄H₉I) through a conical intersection between ³Q₀/¹Q₁ spin-orbit states is revealed by ultrafast XUV transient absorption measuring iodine 4d core-to-valence transitions. The electronic state-sensitivity of the technique allows for a complete mapping of molecular dissociation from photoexcitation to photoproducts. In both molecules, the sub-100 fs transfer of a photoexcited wave packet from the ³Q₀ state into the ¹Q₁ state at the conical intersection is captured. The results show how differences in the electronic state-switching of the wave packet in i-C₃H₇I and t-C₄H₉I directly lead to differences in the photoproduct branching ratio of the two systems.