Simulated photoelectron intensities at the aqueous solution–air interface for flat and cylindrical (microjet) geometries

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

doi:10.1039/c6cp07539h

Cited by 6 publications

(8 citation statements)

References 25 publications

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“…Therefore, when detecting electrons coming from all around the jet, the total spectrum should essentially be a weighted sum of spectra obtained for different angles of the polarization relative to a semi-innite at-surface. 50 However, we found that this polarization direction did not have an important inuence on the simulated spectra, at least when compared to the effects that we demonstrate in this work. Here, we show simulated spectra for three cases, corresponding to 0, 45 and 90 orientations of the polarization.…”

Section: Appendix Cgeometry Approximationscontrasting

confidence: 42%

“…Indeed, the portion of the jet facing the incoming light has this polarization parallel to the surface, while the portion facing the skimmer has it orthogonal to the surface, and all intermediate cases exist. Therefore, when detecting electrons coming from all around the jet, the total spectrum should essentially be a weighted sum of spectra obtained for different angles of the polarization relative to a semi-infinite flat-surface [50]. However, we found that this polarization direction did not have an important influence on the simulated spectra, at least when compared to the effects that we demonstrate in this work.…”

Section: Appendix C -Geometry Approximationsmentioning

confidence: 49%

“…Here, we show simulated spectra for three cases, corresponding to 0, 45 and 90 degrees orientations of the polarization. Other simulations showed a small dependence of spectra on polarization angle (see SI of [8]), and another study concluded that flat-surface and cylindrical experiments produced essentially identical results [50]. Therefore, we kept the simpler semi-infinite flat-surface geometry, with the polarization set orthogonal to the surface.…”

Section: Appendix C -Geometry Approximationsmentioning

confidence: 99%

“…8), and another study concluded that at-surface and cylindrical experiments produced essentially identical results. 50 Therefore, we kept the simpler semi-innite at-surface geometry, with the polarization set orthogonal to the surface.…”

Section: Appendix Cgeometry Approximationsmentioning

confidence: 99%

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Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

et al. 2022

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Section: Appendix Cgeometry Approximationscontrasting

confidence: 42%

Section: Appendix C -Geometry Approximationsmentioning

confidence: 49%

Section: Appendix C -Geometry Approximationsmentioning

confidence: 99%

Section: Appendix Cgeometry Approximationsmentioning

confidence: 99%

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Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

et al. 2022

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“…The AWI is modeled as an atomically flat interface (average emission angle = 0°) following the finding of our recent work, 36 which revealed that the jet curvature has a negligible effect on the ion intensity ratio. The atomic-density profiles obtained from MD simulations are used as input for the sample geometry after coarse graining them into wider bins, since the number of possible layers in SESSA is limited to 54.…”

Section: ■ Methodsmentioning

confidence: 99%

Specific Anion Effects on Na⁺ Adsorption at the Aqueous Solution–Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments

et al. 2017

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Specific ion effects of the large halide anions have been shown to moderate anion adsorption to the air-water interface (AWI), but little quantitative attention has been paid to the behavior of alkali cations. Here we investigate the concentration and local distribution of sodium (Na) at the AWI in dilute (<1 M) aqueous solutions of NaCl, NaBr, and NaI using a combination of molecular dynamics (MD) and SESSA simulations, and liquid jet ambient pressure photoelectron spectroscopy measurements. We use SESSA to simulate Na 2p photoelectron intensities on the basis of the atom density profiles obtained from MD simulations, and we compare the simulation results with photoelectron spectroscopy experiments to evaluate the performance of a nonpolarizable force field model versus that of an induced dipole polarizable one. Our results show that the nonpolarizable force model developed by Horinek and co-workers (Chem. Phys. Lett. 2009, 479, 173-183) accurately predicts the local concentration and distribution of Na near the AWI for all three electrolytes, whereas the polarizable model does not. To our knowledge, this is the first interface-specific spectroscopic validation of a MD force field. The molecular origins of the unique Na distributions for the three electrolytes are analyzed on the basis of electrostatic arguments, and shown to arise from an indirect anion effect wherein the identity of the anion affects the strength of the attractive Na-HO electrostatic interaction. Finally, we use the photoelectron spectroscopy results to constrain the range of inelastic mean free paths (IMFPs) for the three electrolyte solutions used in the SESSA simulations that are able to reproduce the experimental intensities. Our results suggest that earlier estimates of IMFPs for aqueous solutions are likely too high.

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Core-Level Photoelectron Angular Distributions at the Liquid–Vapor Interface

et al. 2023

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Metrics & MoreArticle Recommendations * sı Supporting Information CONSPECTUS: Photoelectron spectroscopy (PES) is a powerful tool for the investigation of liquid−vapor interfaces, with applications in many fields from environmental chemistry to fundamental physics. Among the aspects that have been addressed with PES is the question of how molecules and ions arrange and distribute themselves within the interface, that is, the first few nanometers into solution. This information is of crucial importance, for instance, for atmospheric chemistry, to determine which species are exposed in what concentration to the gas-phase environment. Other topics of interest include the surface propensity of surfactants, their tendency for orientation and self-assembly, as well as ion double layers beneath the liquid−vapor interface. The chemical specificity and surface sensitivity of PES make it in principle well suited for this endeavor. Ideally, one would want to access complete atomic-density distributions along the surface normal, which, however, is difficult to achieve experimentally for reasons to be outlined in this Account. A major complication is the lack of accurate information on electron transport and scattering properties, especially in the kinetic-energy regime below 100 eV, a pre-requisite to retrieving the depth information contained in photoelectron signals.In this Account, we discuss the measurement of the photoelectron angular distributions (PADs) as a way to obtain depth information. Photoelectrons scatter with a certain probability when moving through the bulk liquid before being expelled into a vacuum. Elastic scattering changes the electron direction without a change in the electron kinetic energy, in contrast to inelastic scattering. Random elastic-scattering events usually lead to a reduction of the measured anisotropy as compared to the initial, that is, nascent PAD. This effect that would be considered parasitic when attempting to retrieve information on photoionization dynamics from nascent liquid-phase PADs can be turned into a powerful tool to access information on elastic scattering, and hence probing depth, by measuring core-level PADs. Core-level PADs are relatively unaffected by effects other than elastic scattering, such as orbital character changes due to solvation. By comparing a molecule's gas-phase angular anisotropy, assumed to represent the nascent PAD, with its liquid-phase anisotropy, one can estimate the magnitude of elastic versus inelastic scattering experienced by photoelectrons on their way to the surface from the site at which they were generated. Scattering events increase with increasing depth into solution, and thus it is possible to correlate the observed reduction in angular anisotropy with the depth below the surface along the surface normal.We will showcase this approach for a few examples. In particular, our recent works on surfactant molecules demonstrated that one can indeed probe atomic distances within these molecules with a high sensitivity of ∼1 Å resolution along the ...

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Simulated photoelectron intensities at the aqueous solution–air interface for flat and cylindrical (microjet) geometries

Cited by 6 publications

References 25 publications

Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

Specific Anion Effects on Na⁺ Adsorption at the Aqueous Solution–Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments

Core-Level Photoelectron Angular Distributions at the Liquid–Vapor Interface

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Simulated photoelectron intensities at the aqueous solution–air interface for flat and cylindrical (microjet) geometries

Cited by 6 publications

References 25 publications

Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

Low-energy electron distributions from the photoionization of liquid water: a sensitive test of electron mean free paths

Specific Anion Effects on Na+ Adsorption at the Aqueous Solution–Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments

Core-Level Photoelectron Angular Distributions at the Liquid–Vapor Interface

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Product

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Specific Anion Effects on Na⁺ Adsorption at the Aqueous Solution–Air Interface: MD Simulations, SESSA Calculations, and Photoelectron Spectroscopy Experiments