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revised on 16.09.2019 and posted on 17.09.2019by Alice Kunin, Valerie S. McGraw, Katharine G. Lunny, Daniel Neumark
The dynamics of iodide-uracil-water (I−·U·H2O) clusters following π-π*
excitation of the nucleobase are probed using time-resolved photoelectron
spectroscopy (TRPES). Photoexcitation of this cluster at 4.77 eV results in
electron transfer from the iodide moiety to the uracil, creating a
valence-bound (VB) anion within the cross-correlation of the pump and
probe laser pulses. This species can decay by a number of channels, including
autodetachment and dissociation to I− or larger anion fragments. Comparison
of the energetics of the photoexcited cluster and its decay dynamics with those
of the bare iodide-uracil (I−·U) complex provide a sensitive probe
of the effects of microhydration on these species.