Absolute Electronic Energetics and Quantitative Work Functions of Liquids from Photoelectron Spectroscopy

[Image: see text] Liquid-jet photoelectron spectroscopy (LJ-PES) enabled a breakthrough in the experimental study of the electronic structure of liquid water, aqueous solutions, and volatile liquids more generally. The novelty of this technique, dating back over 25 years, lies in stabilizing a continuous, micron-diameter LJ in a vacuum environment to enable PES studies. A key quantity in PES is the most probable energy associated with vertical promotion of an electron into vacuum: the vertical ionization energy, VIE, for neutrals and cations, or vertical detachment energy, VDE, for anions. These quantities can be used to identify species, their chemical states and bonding environments, and their structural properties in solution. The ability to accurately measure VIEs and VDEs is correspondingly crucial. An associated principal challenge is the determination of these quantities with respect to well-defined energy references. Only with recently developed methods are such measurements routinely and generally viable for liquids. Practically, these methods involve the application of condensed-matter concepts to the acquisition of photoelectron (PE) spectra from liquid samples, rather than solely relying on molecular-physics treatments that have been commonly implemented since the first LJ-PES experiments. This includes explicit consideration of the traversal of electrons to and through the liquid’s surface, prior to free-electron detection. Our approach to measuring VIEs and VDEs with respect to the liquid vacuum level specifically involves detecting the lowest-energy electrons emitted from the sample, which have barely enough energy to surmount the surface potential and accumulate in the low-energy tail of the liquid-phase spectrum. By applying a sufficient bias potential to the liquid sample, this low-energy spectral tail can generally be exposed, with its sharp, low-energy cutoff revealing the genuine kinetic-energy-zero in a measured spectrum, independent of any perturbing intrinsic or extrinsic potentials in the experiment. Together with a precisely known ionizing photon energy, this feature enables the straightforward determination of VIEs or VDEs, with respect to the liquid-phase vacuum level, from any PE feature of interest. Furthermore, by additionally determining solution-phase VIEs and VDEs with respect to the common equilibrated energy level in condensed matter, the Fermi level—the generally implemented reference energy in solid-state PES—solution work functions, eΦ, and liquid-vacuum surface dipole effects can be quantified. With LJs, the Fermi level can only be properly accessed by controlling unwanted surface charging and all other extrinsic potentials, which lead to energy shifts of all PE features and preclude access to accurate electronic energetics. More specifically, conditions must be engineered to minimize all undesirable potentials, while maintaining the equilibrated, intrinsic (contact) potential difference between the sample and apparatus. The establishment of these liquid-phase, accurate energy-referencing protocols importantly enables VIE and VDE determinations from near-arbitrary solutions and the quantitative distinction between bulk electronic structure and interfacial effects. We will review and exemplify these protocols for liquid water and several exemplary aqueous solutions here, with a focus on the lowest-ionization- or lowest-detachment-energy PE peaks, which importantly relate to the oxidative stabilities of aqueous-phase species.