Hydrated Electron Dynamics: From Clusters to Bulk

摘要: The electronic relaxation dynamics of size-selected (H2O)n–/(D2O)n[25 ≤ n 50] clusters have been studied with time-resolved photoelectron imaging. excess electron ( \(e_{c}^{-}\) ) was excited through the \(e_{c}^{-}(p){\leftarrow}e_{c}^{-}(s)\) transition an ultrafast laser pulse, subsequent evolution state monitored photodetachment and All exhibited p-state population decay concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H2O)n– 400 225 (D2O)n–; lifetimes decrease increasing cluster sizes. Our results support “nonadiabatic relaxation” mechanism bulk hydrated \(e_{aq}^{-}\) ), which invokes a 50-femtosecond \(e_{aq}^{-}(p){\rightarrow}e_{aq}^{-}(s^{{\dagger}})\) internal conversion lifetime.