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A Kammrath

Publications and source records attributed to A Kammrath.

3 recordsLinked to original sources

Comment on "Characterization of excess electrons in water-cluster anions by quantum simulations".

The conclusion by Turi et al. (Reports, 5 August 2005, p. 914) that all experimental spectral and energetic data on water-cluster anions point toward surface-bound electrons is overstated. Comparison of experimental vertical detachment energies with their calculated values for (H2O)n- clusters with surface-bound and internalized electrons supports previous arguments that both types of clusters exist.

Comment↗

Observation of large water-cluster anions with surface-bound excess electrons.

Anionic water clusters have long been studied to infer properties of the bulk hydrated electron. We used photoelectron imaging to characterize a class of (H2O)n- and (D2O)n- cluster anions (n </= 200 molecules) with vertical binding energies that are significantly lower than those previously recorded. The data are consistent with a structure in which the excess electron is bound to the surface of the cluster. This result implies that the excess electron in previously observed water-cluster anions, with higher vertical binding energies, was internally solvated. Thus, the properties of those clusters could be extrapolated to those of the bulk hydrated electron.

Journal Article↗

Hydrated electron dynamics: from clusters to bulk.

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.

Journal Article↗