Correction for 'Photoelectron angular distributions as sensitive probes of surfactant layer structure at the liquid-vapor interface' by Rémi Dupuy
et al.
,
Phys. Chem. Chem. Phys.
, 2022,
24
, ...4796-4808,
https://doi.org/10.1039/D1CP05621B
.
Abstract Molecules involved in solvation shells have properties differing from those of the bulk solvent, which can in turn affect reactivity. Among key properties of these molecules are their nature ...and electronic structure. Widely used tools to characterize this type of property are X-ray-based spectroscopies, which, however, usually lack the capability to selectively probe the solvation-shell molecules. A class of X-ray triggered “non-local” processes has the recognized potential to provide this selectivity. Intermolecular Coulombic decay (ICD) and related processes involve neighbouring molecules in the decay of the X-ray-excited target, and are thus naturally sensitive to its immediate environment. Applying electron spectroscopy to aqueous solutions, we explore the resonant flavours of ICD and demonstrate how it can inform on the first solvation shell of excited solvated cations. One particular ICD process turns out to be a potent marker of the formation of ion pairs. Another gives a direct access to the electron binding energies of the water molecules in the first solvation shell, a quantity previously elusive to direct measurements. The resonant nature of the processes makes them readily measurable, providing powerful new spectroscopic tools.
The characterization of liquid-vapor interfaces at the molecular level is an important underpinning for a basic understanding of fundamental heterogeneous processes in many areas, such as atmospheric ...science. Here we use X-ray photoelectron spectroscopy to study the adsorption of a model surfactant, octanoic acid, at the water-gas interface. In particular, we examine the information contained in photoelectron angular distributions and show that information about the relative depth of molecules and functional groups within molecules can be obtained from these measurements. Focusing on the relative location of carboxylate (COO
−
) and carboxylic acid (COOH) groups at different solution pH, the former is found to be immersed deeper into the liquid-vapor interface, which is confirmed by classical molecular dynamics simulations. These results help establish photoelectron angular distributions as a sensitive tool for the characterization of molecules at the liquid-vapor interface.
Photoelectron angular distributions can yield information on the relative depth of different molecular groups at the liquid-vapor interface.
Photoelectron spectroscopy of microjets expanded into vacuum allows access to orbital energies for solute or solvent molecules in the liquid phase. Microjets of water, acetonitrile and alcohols have ...previously been studied; however, it has been unclear whether jets of low temperature molecular solvents could be realized. Here we demonstrate a stable 20 μm jet of liquid ammonia (−60 °C) in a vacuum, which we use to record both valence and core-level band photoelectron spectra using soft X-ray synchrotron radiation. Significant shifts from isolated ammonia in the gas-phase are observed, as is the liquid-phase photoelectron angular anisotropy. Comparisons with spectra of ammonia in clusters and the solid phase, as well as spectra for water in various phases potentially reveal how hydrogen bonding is reflected in the condensed phase electronic structure.
Liquid-jet photoelectron spectroscopy was applied to determine the first acid dissociation constant (pK a) of aqueous-phase glucose while simultaneously identifying the spectroscopic signature of the ...respective deprotonation site. Valence spectra from solutions at pH values below and above the first pK a reveal a change in glucose’s lowest ionization energy upon the deprotonation of neutral glucose and the subsequent emergence of its anionic counterpart. Site-specific insights into the solution-pH-dependent molecular structure changes are also shown to be accessible via C 1s photoelectron spectroscopy. The spectra reveal a considerably lower C 1s binding energy of the carbon site associated with the deprotonated hydroxyl group. The occurrence of photoelectron spectral fingerprints of cyclic and linear glucose prior to and upon deprotonation are also discussed. The experimental data are interpreted with the aid of electronic structure calculations. Our findings highlight the potential of liquid-jet photoelectron spectroscopy to act as a site-selective probe of the molecular structures that underpin the acid–base chemistry of polyprotic systems with relevance to environmental chemistry and biochemistry.
We present spatially resolved measurements of the temperature of a flat liquid water microjet for varying ambient pressures, from vacuum to 100% relative humidity. The entire jet surface is probed in ...a single shot by a high-resolution infrared camera. Obtained 2D images are substantially influenced by the temperature of the apparatus on the opposite side of the infrared camera; a protocol to correct for the thermal background radiation is presented. In vacuum, we observe cooling rates due to water evaporation on the order of 105 K/s. For our system, this corresponds to a temperature decrease in approximately 15 K between upstream and downstream positions of the flowing leaf. Making reasonable assumptions on the absorption of the thermal background radiation in the flatjet, we can extend our analysis to infer a thickness map. For a reference system, our value for the thickness is in good agreement with the one reported from white light interferometry.
Alkali metals in water are always at the brink of explosion. Herein, we show that this vigorous reaction can be kept in a non‐exploding regime, revealing a fascinating richness of hitherto unexplored ...chemical processes. A combination of high‐speed camera imaging and visible/near‐infrared/infrared spectroscopy allowed us to catch and characterize the system at each stage of the reaction. After gently placing a drop of a sodium/potassium alloy on water under an inert atmosphere, the production of solvated electrons became so strong that their characteristic blue color could be observed with the naked eye. The exoergic reaction leading to the formation of hydrogen and hydroxide eventually heated the alkali metal drop such that it became glowing red, and part of the metal evaporated. As a result of the reaction, a perfectly transparent drop consisting of molten hydroxide was temporarily stabilized on water through the Leidenfrost effect, bursting spectacularly after it had cooled sufficiently.
The vigorous reaction of alkali metals in water was kept in a non‐exploding regime through gently placing a drop of Na/K alloy on water. Initially, solvated electrons are produced (blue color), before the exoergic reaction leading to H2 and OH− heats the drop such that it becomes red, and part of the metal evaporates. A transparent drop of molten hydroxide is then temporarily stabilized on the water through the Leidenfrost effect before bursting spectacularly.
The freezing of freely suspended supercooled water droplets with a diameter of bigger than a few micrometers splits into two rather different freezing stages. Within the first very fast dendritic ...freezing stage a spongy network ice with an ice portion of less than one-third forms and more than two-thirds of liquid water remain. In the present work the distribution of the ice portion in the droplet directly after the dendritic freezing phase as well as the evolution of the ice and temperature distribution has been investigated in dependence of the most relevant parameters as droplet diameter, dendritic freezing velocity (which correlates with the supercooling) and heat transfer coefficient to the surroundings (which correlates with the relative droplet velocity compared to the ambient air and with the droplet size). For this purpose on the experimental side acoustically levitated droplets in climate chambers have been investigated in combination with high-speed cameras. The obtained results have been used for finite element method (FEM) simulations of the dendritic freezing phase under consideration of the beginning second, much slower heat-transfer dominated freezing phase. A theoretical model covering 30 layers and 5 shells of the droplet has been developed which allows one to describe the evolution of both freezing phases at the same time. The simulated results are in good agreement with experimental as well as with calculated results exploiting the heat balance equation. The most striking result of this work is the critical radius of the droplet which describes the transition of one-stage freezing of the supercooled water droplet toward the thermodynamically forced dendritical two-stage freezing in which the droplet cannot sufficiently get rid of the formation heat anymore. Depending on the parameters named above this critical radius was found to be in the range of 0.1 to 1 μm by FEM simulation.
We report the first nitrogen 1s Auger–Meitner electron spectrum from a liquid ammonia microjet at a temperature of ∼223 K (–50 °C) and compare it with the simultaneously measured spectrum for ...gas-phase ammonia. The spectra from both phases are interpreted with the assistance of high-level electronic structure and ab initio molecular dynamics calculations. In addition to the regular Auger–Meitner-electron features, we observe electron emission at kinetic energies of 374–388 eV, above the leading Auger–Meitner peak (3a12). Based on the electronic structure calculations, we assign this peak to a shake-up satellite in the gas phase, i.e., Auger–Meitner emission from an intermediate state with additional valence excitation present. The high-energy contribution is significantly enhanced in the liquid phase. We consider various mechanisms contributing to this feature. First, in analogy with other hydrogen-bonded liquids (noticeably water), the high-energy signal may be a signature for an ultrafast proton transfer taking place before the electronic decay (proton transfer mediated charge separation). The ab initio dynamical calculations show, however, that such a process is much slower than electronic decay and is, thus, very unlikely. Next, we consider a non-local version of the Auger–Meitner decay, the Intermolecular Coulombic Decay. The electronic structure calculations support an important contribution of this purely electronic mechanism. Finally, we discuss a non-local enhancement of the shake-up processes.
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