The availability of accurate mean free paths for slow electrons (<50 eV) in water is central to the understanding of many electron-driven processes in aqueous solutions, but their determination poses major challenges to experiment and theory alike. Here, we describe a joint experimental and theoretical study demonstrating a novel approach for testing, and, in the future, refining such mean free paths. We report the development of Monte-Carlo electron-trajectory simulations including elastic and inelastic electron scattering, as well as energy loss and secondary-electron production to predict complete photoelectron spectra of liquid water. These simulations are compared to a new set of photoelectron spectra of a liquid-water microjet recorded over a broad range of photon energies in the extreme ultraviolet (20–57 eV). Several previously published sets of scattering parameters are investigated, providing direct and intuitive insights on how they influence the shape of the low-energy electron spectra. A pronounced sensitivity to the escape barrier is also demonstrated. These simulations considerably advance our understanding of the origin of the prominent low-energy electron distributions in photoelectron spectra of liquid water and clarify the influence of scattering parameters and the escape barrier on their shape. They moreover describe the reshaping and displacement of low-energy photoelectron bands caused by vibrationally inelastic scattering. Our work provides a quantitative basis for the interpretation of the complete photoelectron spectra of liquids and opens the path to fully predictive simulations of low-energy scattering in liquid water.
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