Can Current Experimental Data Exclude Non-Gaussian Genuine Band Shapes in Ultraviolet Photoelectron Spectra of the Hydrated Electron?

Abstract

Two recent articles present results that allegedly exclude a possible multimodal distribution of the hydrated electron in ultraviolet photoelectron spectra. The first article bases its conclusion on the assumption that the non-Gaussian genuine band shape previously retrieved for the solvated electron in liquid water is an artifact arising from insufficient electron scattering cross sections used in the retrieval. The second article excludes a multimodal band shape based on a photoelectron spectrum of the solvated electron in water clusters recorded at a single ultraviolet photon energy, and it further assumes that cluster results are transferable to the liquid without further justification. Here, we show that based on current data multimodal distributions cannot be unambiguously excluded. Furthermore, the transferability of cluster results to the liquid can be neither justified nor refuted on the basis of currently available experimental ultraviolet photoelectron spectra.