Structure of the hexamer anion extracted from previous analysis of the vibrational spectra (Refs. 27 and 29) shown along with a contour (0.015) of the excess electron molecular orbital. The labels AA, AAD, ADD, and AD refer to the number of donor and acceptor H bonds associated with each water molecule location. The darker isosurface corresponds to the contour of the wave function opposite in phase to that of the diffuse lobe.
Vibrational action spectra of selected clusters in the range. The spectra were monitored by electron photodetachment, while the spectra correspond to photoevaporation of a water monomer from the parent ion. Labels and indicate assignments of the strong peaks in the spectrum to the symmetric and asymmetric OH stretches, respectively, of the AA water molecule (see Fig. 1) (Ref. 29). The and bands correspond mostly to stretches of dangling OH groups in the hexamer anion which undergo significant interaction with the diffuse electron. The specific hydrogen atom locations are labeled in Fig. 1. The F bands are assigned to noninteracting free OH stretches. See text for discussion of bands labeled and .
Comparison of the predissociation spectra for (a) , (b) , and (c) . The labels AD and AAD in (c) denote water molecules in acceptor-donor and acceptor-acceptor-donor H-bonding sites, respectively. The gray line in (a) displays the infrared absorption spectrum of liquid water for reference.
Evolution of the various vibrational band positions identified in Fig. 2 as a function of cluster size. See Fig. 2 caption for label definitions.
Calculated molecular orbitals and structures highlighting the vibrational dependence of the excess electron orbital. The contours (0.015) in panel (a) correspond to the (classical) inner and outer turning points of the AA symmetric stretch vibration. Panel (b) represents the difference contour (0.0013) between these orbitals, emphasizing the degree to which the wave function is distorted along the vibrational coordinate.
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