Quantitative electronic structure and work-function changes of liquid water induced by solute

Recent advancement in quantitative liquid-jet photoelectron spectroscopy enables the accurate determination of the absolute-scale electronic energetics of liquids and species in solution. The major objective of the present work is the determination of the absolute lowest-ionization energy of liquid water, corresponding to the 1b₁ orbital electron liberation, which is found to vary upon solute addition, and depends on the solute concentration. We discuss two prototypical aqueous salt solutions, NaI_(aq) and tetrabutylammonium iodide, TBAI_(aq), with the latter being a strong surfactant. Our results reveal considerably different behavior of the liquid water 1b₁ binding energy in each case. In the NaI_(aq) solutions, the 1b₁ energy increases by about 0.3 eV upon increasing the salt concentration from very dilute to near-saturation concentrations, whereas for TBAI the energy decreases by about 0.7 eV upon formation of a TBAI surface layer. The photoelectron spectra also allow us to quantify the solute-induced effects on the solute binding energies, as inferred from concentration-dependent energy shifts of the I^- 5p binding energy. For NaI_(aq), an almost identical I^- 5p shift is found as for the water 1b₁ binding energy, with a larger shift occurring in the opposite direction for the TBAI_(aq) solution. We show that the evolution of the water 1b₁ energy in the NaI_(aq) solutions can be primarily assigned to a change of water's electronic structure in the solution bulk. In contrast, apparent changes of the 1b₁ energy for TBAI_(aq) solutions can be related to changes of the solution work function which could arise from surface molecular dipoles. Furthermore, for both of the solutions studied here, the measured water 1b₁ binding energies can be correlated with the extensive solution molecular structure changes occurring at high salt concentrations, where in the case of NaI_(aq), too few water molecules exist to hydrate individual ions and the solution adopts a crystalline-like phase. We also comment on the concentration-dependent shape of the second, 3a₁ orbital liquid water ionization feature which is a sensitive signature of water-water hydrogen bond interactions.