Pre-Dewar structure modulates protonated azaindole photodynamics.

Recent experimental work revealed that the lifetime of the S state of protonated 7-azaindole is about ten times longer than that of protonated 6-azaindole. We simulated the nonradiative decay pathways of these molecules using trajectory surface hopping dynamics after photoexcitation into S to elucidate the reason for this difference. Both isomers mainly follow a common ππ* relaxation pathway involving multiple state crossings while coming down from S to S in the subpicosecond time scale. However, the simulations reveal that the excited-state topographies are such that while the 6-isomer can easily access the region of nonadiabatic transitions, the internal conversion of the 7-isomer is delayed by a pre-Dewar bond formation with a boat conformation.