Ultrafast Dynamics of Electrons in Ammonia

• Published in: Annual review of physical chemistry Vol. 66; no. 1; pp. 97 - 118
• Main Author: Vöhringer, Peter
• Format: Journal Article
• Language: English
• Published: United States Annual Reviews 01.04.2015; Annual Reviews, Inc
• Subjects: Ammonia; Chemical properties; Electrochemistry; Electrons; femtosecond spectroscopy; Ionization; liquids and supercritical fluids; metal-ammonia solutions; Metals; Optical properties; photoionization; proton-coupled electron transfer; solvated electrons; Solvents; Spectroscopy; femtosecond spectroscopy; liquids and supercritical fluids; solvated electrons; proton-coupled electron transfer; photoionization; metal-ammonia solutions
• ISSN: 0066-426X; 1545-1593
• DOI: 10.1146/annurev-physchem-040214-121228

Solvated electrons were first discovered in solutions of metals in liquid ammonia. The physical and chemical properties of these species have been studied extensively for many decades using an arsenal of electrochemical, spectroscopic, and theoretical techniques. Yet, in contrast to their hydrated counterpart, the ultrafast dynamics of ammoniated electrons remained completely unexplored until quite recently. Femtosecond pump-probe spectroscopy on metal-ammonia solutions and femtosecond multiphoton ionization spectroscopy on the neat ammonia solvent have provided new insights into the optical properties and the reactivities of this fascinating species. This article reviews the nature of the optical transition, which gives the metal-ammonia solutions their characteristic blue appearance, in terms of ultrafast relaxation processes involving bound and continuum excited states. The recombination processes following the injection of an electron via photoionization of the solvent are discussed in the context of the electronic structure of the liquid and the anionic defect associated with the solvated electron.