Despite the ubiquitous nature of aqueous solutions across the chemical, biological and environmental sciences our experimental understanding of their electronic structure is rudimentary-qualitative at best. One of the most basic and seemingly straightforward properties of aqueous solutions-ionization energies-are (qualitatively) tabulated at the water-air interface for a mere handful of solutes, and the manner in which these results are obtained assume the aqueous solutions behave like a gas in the photoelectron experiment (where the vacuum levels of the aqueous solution and of the photoelectron analyzer are equilibrated). Here we report the experimental measure of a sizeable offset (ca. 0.6 eV) between the vacuum levels of an aqueous solution (0.05 M NaCl) and that of our photoelectron analyzer, indicating a breakdown of the gas-like vacuum level alignment assumption for the aqueous solution. By quantifying the vacuum level offset as a function of solution chemical composition our measurements enable, for the first time, quantitative determination of ionization energies in liquid solutions. These results reveal that the ionization energy of liquid water is not independent of the chemical composition of the solution as is usually inferred in the literature, a finding that has important ramifications as measured ionization energies are frequently used to validate theoretical models that posses the ability to provide microscopic insight not directly available by experiment. Finally, we derive the work function, or the electrochemical potential of the aqueous solution and show that it too varies with the chemical composition of the solution.
Over the past decade, energy-dependent ambient pressure X-ray photoelectron spectroscopy (AP-XPS) has emerged as a powerful analytical probe of the ion spatial distributions at the vapor (vacuum)-aqueous electrolyte interface. These experiments are often paired with complementary molecular dynamics (MD) simulations in an attempt at to provide a complete description of the liquid interface. There is, however, no systematic protocol that permits a straightforward comparison of the two sets of results. XPS is an integrated technique that averages signals from multiple layers in a solution even at the lowest photoelectron kinetic energies routinely employed, whereas MD simulations provide a microscopic layer-by-layer description of the solution composition near the interface. Here we use the National Institute of Standards and Technology database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to quantitatively interpret atom-density profiles from MD simulations for XPS signal intensities using sodium and potassium iodide solutions as examples. We show that electron inelastic mean free paths calculated from a semi-empirical formula depend strongly on solution composition, varying by up to 30 % between pure water and concentrated NaI. The XPS signal thus arises from different information depths in different solutions for a fixed photoelectron kinetic energy. XPS signal intensities are calculated using SESSA as a function of photoelectron kinetic energy (probe depth) and compared with a widely employed ad hoc method. SESSA simulations illustrate the importance of accounting for elastic scattering events at low photoelectron kinetic energies (< 300 eV) where the ad hoc method systematically underestimates the preferential enhancement of anions over cations. Finally, some technical aspects of applying SESSA to liquid interfaces are discussed.
The atomic layer deposition (ALD) of TiO 2 on a RuO 2 (110) surface from tetrakis(dimethylamido) titanium and water at 110°C was investigated using near ambient pressure Xray photoelectron spectroscopy (NAP-XPS) at precursor pressures up to 0.1 mbar. In addition to the expected cyclic surface species, evidence for side reactions was found. Dimethylamine adsorbs on the surface during the TDMAT half-cycle, and a second species, likely methyl methylenimine, also forms. The removal of the amide ligand and the formation of an alkyammonium species during the water half-cycle were found to be pressure dependent. The O 1s, Ru 3d, and Ti 2p spectra show the formation of the Ru−O−Ti interface, and the binding energies are consistent with formation of TiO 2 after one full ALD cycle. Dosing TDMAT on the RuO 2 (110) surface at room temperature promotes a multilayer formation that begins to desorb at 40°C. The imine species is not seen until 60°C. These insights into the ALD mechanism and precursor pressure dependence on reactivity highlight the utility of NAP-XPS in studying ALD processes and interface formation.
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