(a) Diagram of the processes involved in excited state relaxation of the condensed phase hydrated electron. The red arrow represents the pump laser pulse, while black curves represent the s-like ground state and p-like excited state of the hydrated electron. Various dynamical processes discussed in the text are labeled and diagramed with dashed black arrows. (b) Diagram of the photodetachment processes observed in large anionic water clusters. The black curves show the ground and excited states of the cluster, while the dashed line represents the threshold for vertical detachment. Blue arrows represent the probe laser pulse, while the red arrow represents the pump pulse.
Time-resolved photoelectron spectra of (a) and (b) presented as waterfall plots, with time delay increasing from back to front. Features are labeled A and B with reference to Fig. 1(b).
(a) Integrated intensity of features A (black squares) and B (red circles) at each time delay for . Each plot has been normalized on a zero to one scale. Typical data sets exhibit maximum depletion of feature A. Best fit lines, as outlined in Sec. IV, are also shown. In addition, the integrated intensity of feature A, normalized on a zero to one scale, is shown inverted (blue triangles) for comparison. (b) Integrated intensities of feature B for (black squares), (red circles), and (blue triangles) are plotted against time delay, normalized on a zero to one scale, along with best fit lines. (c) Integrated intensity of three eKE sections of feature B for . The integration range for each section is defined in the inset, with I (black squares) integrated from 1.7 to 2.0 eV, II (red circles) integrated from 2.0 to 2.4 eV, and III (blue triangles) integrated from 2.4 to 2.9 eV. Connecting lines are shown in corresponding color as a guide to the eye.
IC lifetimes, , for (red circles) and (black squares) plotted against cluster size (1/n). Error bars presented represent standard error from averaging of two to three experiments at each cluster size. For cluster sizes where only one experiment was performed, the standard error resulting from the fitting routine is shown. Linear fits of all data points for are shown as dotted lines and for data points with as solid lines, in red for and black for . The dotted lines have been extended to in order to facilitate comparison with the large cluster data.
(a) Mean eKE of feature B (, black squares) for , along with the integrated intensity of feature B (red circles) plotted against time delay. (b) Mean eKE of feature A (, black squares) for , along with the integrated intensity of feature B (red circles) plotted against time delay. Connecting lines in both panels are shown in corresponding color as a guide to the eye.
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