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Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions



Cedric J. Powell, Giorgia Olivieri, Krista Parry, Douglas Tobias, Matthew Brown


Over the past decade, energy-dependent X-ray photoelectron spectroscopy (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 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 (
Journal of Chemical Physics


alkali halides, aqueous solutions, molecular dynamics simulations, surface analysis, x-ray photoelectron spectroscopy


Powell, C. , Olivieri, G. , Parry, K. , Tobias, D. and Brown, M. (2016), Quantitative interpretation of molecular dynamics simulations for X-ray photoelectron spectroscopy of aqueous solutions, Journal of Chemical Physics, [online], (Accessed June 15, 2024)


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Created April 19, 2016, Updated January 27, 2020