Hydrated electron dynamics: from clusters to bulk
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Updated: Jul 29, 2026

Spatial Separation of Molecular Conformers and Clusters
Published on: January 9, 2014
A E Bragg1, J R R Verlet, A Kammrath
1Department of Chemistry, University of California, Berkeley, CA 94720, USA.
Abstract:
The electronic relaxation dynamics of size-selected (H2O)n-/(D2O)n[25 = n = 50] clusters have been studied with time-resolved photoelectron imaging. The excess electron (ec-) was excited through the ec-(p)<--ec-(s) transition with an ultrafast laser pulse, with subsequent evolution of the excited state monitored with photodetachment and photoelectron imaging. All clusters exhibited p-state population decay with concomitant s-state repopulation (internal conversion) on time scales ranging from 180 to 130 femtoseconds for (H2O)n- and 400 to 225 femtoseconds for (D2O)n-; the lifetimes decrease with increasing cluster sizes. Our results support the "nonadiabatic relaxation" mechanism for the bulk hydrated electron (eaq-), which invokes a 50-femtosecond eaq-(p)-->eaq-(s(dagger)) internal conversion lifetime.
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