On the nature and signatures of the solvated electron in water

The hydrated electron is one of the simplest chemical transients and has been the subject of intense investigation and speculation since its discovery in 1962 by Hart and Boag. Although extensive kinetic and spectroscopic research on this species has been reported for many decades, its structure, i.e., the dominant electron-water binding motif, and its binding energy remained uncertain. A recent milestone in the research on the hydrated electron was the determination of its binding energy by liquid-jet photoelectron spectroscopy. It turned out that the assumption of a single electron binding motif in liquid water is an oversimplification. In addition to different isomers in cluster spectroscopy and different transient species of unknown structure in ultrafast experiments, long-lived hydrated electrons near the surface of liquid water have recently been discovered. The present article gives an account of recent work on the topic solvated electrons'' from the perspectives of cluster spectroscopy, condensed-phase spectroscopy, as well as theory. It highlights and critically discusses recent findings and their implications for our understanding of electron solvation in aqueous environments.