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.

A rechargeable aluminum-ion battery based on chloroaluminate electrolytes has received intense attention due to the high abundance and chemical stability of aluminum. However, the fundamental intercalation processes and dynamics in these battery systems remain unresolved. Here, the energetics and dynamics of chloroaluminate ion intercalation in atomically thin single crystal graphite are investigated by fabricating mesoscopic devices for charge transport and operando optical microscopy. These mesoscopic measurements are compared to the high-performance rechargeable Al-based battery consisting of a few-layer graphene–multiwall carbon nanotube composite cathode. These composites exhibit a 60% capacity enhancement over pyrolytic graphite, while an ∼3-fold improvement in overall ion diffusivity is also obtained exhibiting ∼1% of those in atomically thin single crystals. Our results thus establish the distinction between intrinsic and ensemble electrochemical behavior in Al-based batteries and show that engineering ion transport in these devices can yet lead to vast improvements in battery performance.

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. The results are also compared with TRPES experiments on I⁻·U·H₂O at lower pump photon energies, where both the initial photoinduced dynamics and the decay of the photoexcited cluster are qualitatively different.

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.

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.