Photoelectron processes in liquid water: new methods for probing elementary reactivity*

In the condensed phase, intermolecular interactions often control chemical reactivity but are complex to quantify. Understanding how the electronic structure of an aqueous solute is intricately bound up with the arrangement of the host liquid provides insight into how reactions are influenced by the environment in which they take place. Our group has exploited liquid-jet photoelectron spectroscopy to learn about the orbital energies and shapes for water as well as for textbook aqueous inorganic ions in the bulk and at the air/water interface. With femtosecond time resolution, the non-equilibrium evolution of the valence orbitals involved in excited state and redox reactions can then be tracked.