Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries

Saak, Clara‐Magdalena; Richter, Clemens; Unger, I.; Mucke, Melanie; Nicolas, Christophe; Hergenhahn, U.; Caleman, Carl; Huttula, Marko; Patanen, Minna; Björneholm, Olle

doi:10.1039/c9cp06661f

Cited by 3 publications

(6 citation statements)

References 42 publications

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“…The threshold energies were obtained from extrapolated line fits to the low BE side, as shown in the inset on the top right corner of Figure . With a similar treatment, for liquid water, a threshold BE of 9.9 eV was found by Winter et al, while 10.12(15) eV was found by Perry et al The VBEs in our experiment are among the lowest reported for water clusters (see, e.g., refs , and references therein for values by others), and settle between the reported bulk liquid values. Based on the here still resolved VBE shift between the two sizes, and the trend of results from various other experiments compiled by Gartmann et al, we expect that the VBE of our (larger) pure water clusters is still up to a couple of hundred meV above the asymptotic bulk limit.…”

Section: Resultssupporting

confidence: 88%

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

et al. 2021

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The solvation of alkali and halide ions in the aqueous environment has been a subject of intense experimental and theoretical research with multidisciplinary interests; yet, a comprehensive molecular-level understanding has still not been obtained. In recent years, electron spectroscopy has been increasingly applied to study the electronic and structural properties of aqueous ions with implications, especially in atmospheric chemistry. In this work, we report core and valence level (Cl 2p, Cl 3p, and K 3p) photoelectron spectra of the common alkali halide, KCl, doped in gas-phase water clusters in the size range of a few hundred water molecules. The results indicate that the electronic structure of these nanosolutions shows a distinct character from that observed at the liquid–vapor interface in liquid microjets and ambient pressure setups. Insights are provided into the unique solvation properties of ions in a nanoaqueous environment, emerging properties of bulk electrolyte solutions with growing cluster size, and sensitivity of the electronic structure to varying solvation configurations.

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Section: Resultssupporting

confidence: 88%

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

et al. 2021

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“…One may ask whether this signature is sufficiently robust to be used as an indicator for hydrogen bonding, thus reversing the arguments made in the initial study. In investigations on clusters of water and heavy water, the spectral feature due to PTM-ICD could be seen in analogy to liquid water . Differences between the two respective traces were more pronounced in larger clusters.…”

Section: Systems and Applicationsmentioning

confidence: 86%

“…In investigations on clusters of water and heavy water, the spectral feature due to PTM-ICD could be seen in analogy to liquid water. 505 Differences between the two respective traces were more pronounced in larger clusters. A quantitative metric for the spectral difference was established by the authors, according to which the H-bonding related PTM-ICD signature is in large clusters as strong as in liquid water, within the accuracy of the experiment.…”

Section: Systems and Applicationsmentioning

confidence: 94%

“…This is borne out by the quantitative analysis of the spectral difference, resulting in a value of 0.40(9) for bulk methanol relative to liquid water, and in slightly lower values for methanol clusters of different size. 505 …”

Section: Systems and Applicationsmentioning

confidence: 99%

“…Visually, the effect appears to be less pronounced, which seems explicable as each oxygen center in methanol is only singly bonded, while in water it accepts two H-bonds. This is borne out by the quantitative analysis of the spectral difference, resulting in a value of 0.40(9) for bulk methanol relative to liquid water, and in slightly lower values for methanol clusters of different size …”

Section: Systems and Applicationsmentioning

confidence: 99%

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Interatomic and Intermolecular Coulombic Decay

et al. 2020

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Interatomic or intermolecular Coulombic decay (ICD) is a nonlocal electronic decay mechanism occurring in weakly bound matter. In an ICD process, energy released by electronic relaxation of an excited atom or molecule leads to ionization of a neighboring one via Coulombic electron interactions. ICD has been predicted theoretically in the mid nineties of the last century, and its existence has been confirmed experimentally approximately ten years later. Since then, a number of fundamental and applied aspects have been studied in this quickly growing field of research. This review provides an introduction to ICD and draws the connection to related energy transfer and ionization processes. The theoretical approaches for the description of ICD as well as the experimental techniques developed and employed for its investigation are described. The existing body of literature on experimental and theoretical studies of ICD processes in different atomic and molecular systems is reviewed.

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Radiationless decay spectrum of O 1s double core holes in liquid water

Trinter,

Inhester,

Püttner

et al. 2024

The Journal of Chemical Physics

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We present a combined experimental and theoretical investigation of the radiationless decay spectrum of an O 1s double core hole in liquid water. Our experiments were carried out using liquid-jet electron spectroscopy from cylindrical microjets of normal and deuterated water. The signal of the double-core-hole spectral fingerprints (hypersatellites) of liquid water is clearly identified, with an intensity ratio to Auger decay of singly charged O 1s of 0.0014(5). We observe a significant isotope effect between liquid H2O and D2O. For theoretical modeling, the Auger electron spectrum of the central water molecule in a water pentamer was calculated using an electronic-structure toolkit combined with molecular-dynamics simulations to capture the influence of molecular rearrangement within the ultrashort lifetime of the double core hole. We obtained the static and dynamic Auger spectra for H2O, (H2O)5, D2O, and (D2O)5, instantaneous Auger spectra at selected times after core-level ionization, and the symmetrized oxygen-hydrogen distance as a function of time after double core ionization for all four prototypical systems. We consider this observation of liquid-water double core holes as a new tool to study ultrafast nuclear dynamics.

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Proton dynamics in molecular solvent clusters as an indicator for hydrogen bond network strength in confined geometries

Abstract: The size-dependence of proton-dynamics occurring upon core-ionisation is linked to a weakening of the hydrogen-bond network in molecular clusters.

Cited by 3 publications

References 42 publications

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

Core and Valence Level Photoelectron Spectroscopy of Nanosolvated KCl

Interatomic and Intermolecular Coulombic Decay

Radiationless decay spectrum of O 1s double core holes in liquid water

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