Photoelectron Spectroscopy of Large Water Cluster Anions

Photoelectron spectra of large size selected water cluster anions (H2O)(n)(-) (n = 100-1100) have been measured at a low cluster temperature (80 K). An extensive peak analysis has been conducted in order to determine average and isomer-resolved vertical detachment energies (VDE) of the hydrated electron. This allows us, in combination with the reevaluated data of the previously reported results on small- and medium-sized water cluster anions (J. Chem. Phys. 2009, 131, 144303), to draw a comprehensive picture of the size-dependent development of the VDEs of water clusters. This allows for an improved extrapolation of the cluster VDEs to the bulk, which yields a value of 3.60 +/- 0.03 eV. The general size dependence of the VDEs is in very good agreement with a standard dielectric model.

Automated summary

The photoelectron spectra of large size selected water cluster anions were measured to determine the average and isomer-resolved vertical detachment energies of the hydrated electron. By combining with previous data on small- and medium-sized water cluster anions, a comprehensive picture of the size-dependent development of the vertical detachment energies of water clusters was drawn. The extrapolation of cluster vertical detachment energies to the bulk was improved, yielding a value of 3.60 +/- 0.03 eV, in good agreement with a standard dielectric model.