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Conical intersections between electronic states often dictate the chemistryof photoexcited molecules. Recently developed sources of ultrashort extremeultraviolet (XUV) pulses tuned to element-specific transitions in moleculesallow for the unambiguous detection of electronic state-switching at a conicalintersection. Here, the fragmentation of photoexcited iso-propyl iodide andtert-butyl iodide molecules (i-C$_{3}$H$_{7}$I and t-C$_{4}$H$_{9}$I) through aconical intersection between $^{3}$Q$_{0}$/$^{1}$Q$_{1}$ spin-orbit states isrevealed by ultrafast XUV transient absorption measuring iodine 4dcore-to-valence transitions. The electronic state-sensitivity of the techniqueallows for a complete mapping of molecular dissociation from photoexcitation tophotoproducts. In both molecules, the sub-100 fs transfer of a photoexcitedwave packet from the $^{3}$Q$_{0}$ state into the $^{1}$Q$_{1}$ state at theconical intersection is captured. The results show how differences in theelectronic state-switching of the wave packet in i-C$_{3}$H$_{7}$I andt-C$_{4}$H$_{9}$I directly lead to differences in the photoproduct branchingratio of the two systems.

Revealing electronic state-switching at conical intersections in alkyl iodides by ultrafast XUV transient absorption spectroscopy