Edmund Leary, Horst Höbenreich, Simon J. Higgins et al. · Physical Review Letters · 2009
We present a new route to single-molecule sensing via solvation shells surrounding a current-carrying backbone molecule. As an example, we show that the presence of a water solvation shell "gates" the conductance of a family of oligothiophene-containing molecular wires, and that the longer the oligothiophene, the larger is the effect. For the longest example studied, the molecular conductance is over 2 orders of magnitude larger in the presence of a shell comprising just 10 water molecules. A first principles theoretical investigation of electron transport through the molecules, using the nonequilibrium Green's function method, shows that water molecules interact directly with the thiophene rings, significantly shifting transport resonances and greatly increasing the conductance. This reversible effect is confirmed experimentally through conductance measurements performed in the presence of moist air and dry argon.
Cited by 93
Xin Xin, Xiao Niu, Wanqi Liu et al. · ChemPhysChem · 2020
We present a hybrid solvation model with first solvation shell to calculate solvation free energies. This hybrid model combines the quantum mechanics and molecular mechanics methods with the analytical expression based on the Born solvation model to calculate solvation free energies. Based on calculated free energies of solvation and reaction profiles in gas phase, we set up a unified scheme to predict reaction profiles in solution. The predicted solvation free energies and reaction barriers are compared with experimental results for twenty bimolecular nucleophilic substitution reactions. These comparisons show that our hybrid solvation model can predict reliable solvation free energies and reaction barriers for chemical reactions of small molecules in aqueous solution.
Cited by 8
A. BOTTI, BRUNI, Fabio, S. IMBERTI et al. · Iris (Roma Tre University) · 2005
Cited by 0
A. BOTTI, S. IMBERTI, RICCI, Maria Antonietta et al. · Iris (Roma Tre University) · 2004
Cited by 0
Marco Masia, Rossend Rey · The Journal of Chemical Physics · 2005
It is shown that, for a tightly bound ion-solvation shell complex, the mean square displacement for solvation molecules is characterized by a long lasting transitory. This initial portion is related to the rotational relaxation of the complex and can reach up to several hundred picoseconds for a representative example such as the Mg(2+) ion in water. As the diffusion coefficient is usually fitted using much shorter time spans, unnoticed overestimations are possible. It is argued that, instead of computing the aforementioned diffusion coefficient from the mean square displacement, it should be defined taking as a basic guideline the ratio between the rotational relaxation time of the complex and the lifetime within the first solvation shell.
Cited by 13
H. G. Hertz · Angewandte Chemie International Edition in English · 1970
Abstract The first part of the article deals with the structure of the solvation shell of simple ions, particularly those with the inert gas structure, in aqueous and non‐aqueous solution. It is nowadays possible in favorable cases, to determine the solvation number or the coordination number in the first sphere. The solvation shells appear to be “more liquid” than was formerly believed. The hydration of neutral inert particles in aqueous solution is discussed in the second part. Caution is advised in the postulation of particular structural arrangements in the solution.
Cited by 45
И. В. Шаманин, М. A. Kazaryan, С. Н. Тимченко et al. · Bulletin of the Lebedev Physics Institute · 2017
The eigenfrequencies of solvation shell oscillations with respect to the ion are estimated in various approximations describing the ion–solvation shell system. The results of comparisonwith experiments suggest that the most appropriate is the model in which the solvated ion is considered to be a spherical rotator formed either by the entire solvation shell or by a layer of solvent molecules adjacent to the outer boundary of the solvation shell.
Cited by 5
Larry Kevan · The Journal of Chemical Physics · 1978
Silver atom hydralic in acqueous glasses is studied by electron spin resonance. Shell geometry for Ag atom solvation in ice matrix is explained. (AIP)
Cited by 12
Eirik F. da Silva, Hallvard F. Svendsen, Kenneth M. Merz · The Journal of Physical Chemistry A · 2009
A method is presented to explicitly represent the first solvation shell in continuum solvation calculations. Initial solvation shell geometries were generated with classical molecular dynamics simulations. Clusters consisting of solute and 5 solvent molecules were fully relaxed in quantum mechanical calculations. The free energy of solvation of the solute was calculated from the free energy of formation of the cluster, and the solvation free energy of the cluster was calculated with continuum solvation models. The method has been implemented with two continuum solvation models, a Poisson-Boltzmann model and the IEF-PCM model. Calculations were carried out for a set of 60 ionic species. Implemented with the Poisson-Boltzmann model the method gave an unsigned average error of 2.1 kcal/mol and a rmsd of 2.6 kcal/mol for anions; for cations the unsigned average error was 2.8 kcal/mol and the rmsd 3.9 kcal/mol. Similar results were obtained with the IEF-PCM model.
Cited by 126Open access
Rémi Dupuy, Tillmann Buttersack, Florian Trinter et al. · Nature Communications · 2024
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.
Cited by 8Open access
M.A. Orekhov · Vestnik Obedinennogo instituta vysokikh temperatur · 2022
Cited by 0
Dupuy, Remi, Buttersack, Tillmann, Trinter, Florian et al. · DESY Publication Database (PUBDB) (Deutsches Elektronen-Synchrotron) · 2024
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.
Cited by 0Open access
Eirik F. da Silva (1924027), Hallvard F. Svendsen (1792027), Kenneth M. Merz (1311057) · Figshare · 2016
A method is presented to explicitly represent the first solvation shell in continuum solvation calculations. Initial solvation shell geometries were generated with classical molecular dynamics simulations. Clusters consisting of solute and 5 solvent molecules were fully relaxed in quantum mechanical calculations. The free energy of solvation of the solute was calculated from the free energy of formation of the cluster, and the solvation free energy of the cluster was calculated with continuum solvation models. The method has been implemented with two continuum solvation models, a Poisson−Boltzmann model and the IEF-PCM model. Calculations were carried out for a set of 60 ionic species. Implemented with the Poisson−Boltzmann model the method gave an unsigned average error of 2.1 kcal/mol and a rmsd of 2.6 kcal/mol for anions; for cations the unsigned average error was 2.8 kcal/mol and the rmsd 3.9 kcal/mol. Similar results were obtained with the IEF-PCM model.
Cited by 0Open access
Ee C. Chambers, Gregory D. Hawkins, Christopher J. Cramer et al. · 1996
Cited by 0
K. Rebecca Fega, Avid Scott Wilcox, Dor Ben‐Amotz · Applied Spectroscopy · 2012
Raman spectroscopy and multivariate curve resolution (Raman-MCR) are combined to yield a powerful spectroscopic method for identifying solute-induced perturbations of solvent molecules. The principles and applications of the resulting solvation-shell spectroscopy are described and illustrated using both numerical model spectra and experimental Raman spectra, including water in acetone and aqueous OH(-), as well as of both neutral and ionic acetic acid solutions. The results illustrate the quantitative capabilities of Raman-MCR as a solvation-shell spectroscopy, including fundamental limitations arising from "intensity" and "rotational" ambiguities.
Cited by 64
Dupuy, Rémi, Buttersack, Tillmann, Trinter, Florian et al. · Zenodo (CERN European Organization for Nuclear Research) · 2024
Dataset pertaining to the article "The solvation shell probed by resonant intermolecular Coulombic decay", accepted for publication in Nature Communications. Here, we show how a resonant variant of intermolecular Coulombic decay can be used to selectively infer information on the electronic structure of solvent shell molecules around a metal ion in aqueous solution. Experiments were done using a liquid microjet. Files with extension .nxs are hdf5-files structured according to the NeXus standard v2022.07, seehttps://www.nexusformat.org/https://fairmat-experimental.github.io/nexus-fairmat-proposal/50433d9039b3f33299bab338998acb5335cd8951/mpes-structure.htmlNeXus data files can be opened with any software capable of opening hdf5-structured files. The following viewers are adapted to the specifics of the NeXus data format:* nexpy (distributed with python)* https://h5web.panosc.eu/h5wasm (web-based NeXus viewer maintained by the European Photon and Neutron Open Science Cloud-consortium) In each NeXus file-entry, two types of spectra are shown:1. Sweep-averaged spectra, integrated over the non-dispersive coordinate of our detector ('data').2. As-measured data ('raw'). Files with extension .txt are tab-separated ascii-files. Files with exension .zip are zipped archives of several .txt-files. The following files are provided: Photoemission data pertaining to all figures in the article's main text and supplementary information, including all relevant metadata:CaICD_dataset.nxs Numeric representations of the traces shown in the article's and supplementary information's figures, one zipped archive per figure:FigN.zip Version history1: initial upload Contact persons for questions regarding this data set: Rémi Dupuy, remi.dupuy@sorbonne-universite.fr; Uwe Hergenhahn, uhe@fhi.mpg.de. If you use these data for your scientific work we are curious to learn about it.
Cited by 0Open access
Xiangwen Wang, Dimitrios Toroz, Seonmyeong Kim et al. · ChemRxiv · 2020
<div> <p>As natural aqueous solutions are far from being pure water, being rich in ions, the properties of solvated ions are of relevance for a wide range of systems, including biological and geochemical environments. We conducted ab initio and classical MD simulations of the alkaline earth metal ions Mg<sup>2+</sup> and Ca<sup>2+</sup> and of the alkali metal ions Li<sup>+</sup>, Na<sup>+</sup>, K<sup>+</sup> and Cs<sup>+</sup> in pure water and electrolyte solutions containing the counterions Cl<sup>–</sup> and SO<sub>4</sub><sup>2–</sup>. Through a detailed analysis of these simulations, this study reports on the effect of solution chemistry (composition and concentration of the solution) to the ion–water structural properties and interaction strength, and to the dynamics, hydrogen bond network, and low-frequency dynamics of the ionic solvation shell. Except for the ion–water radial distribution function, which is weakly dependent on the counter-ions and concentrations, we found that all other properties can be significantly influenced by the chemical characteristics of the solution. Calculation of the velocity autocorrelation function of magnesium ions, for example, shows that chlorine ions located in the second coordination shell of Mg<sup>2+</sup> weaken the Mg(H<sub>2</sub>O)<sub>6</sub><sup>2+</sup> hydration ‘cage’ of the cation. The result reported in this study suggest that ionic solvation shell can be significantly influenced by the interactions between other ions present in solution ions, especially those of opposite charge. In more general terms, the chemical characteristics of the solution, including the balance between ion-solvent and ion-ion interactions, could result in significant differences in behavior and function of the ionic solvation shell.</p> </div>
Cited by 0Open access
Mazin Nasralla, Harrison Laurent, Oliver L. G. Alderman et al. · Proceedings of the National Academy of Sciences · 2024
Trimethylamine-N-oxide (TMAO) and urea are metabolites that are used by some marine animals to maintain their cell volume in a saline environment. Urea is a well-known denaturant, and TMAO is a protective osmolyte that counteracts urea-induced protein denaturation. TMAO also has a general protein-protective effect, for example, it counters pressure-induced protein denaturation in deep-sea fish. These opposing effects on protein stability have been linked to the spatial relationship of TMAO, urea, and protein molecules. It is generally accepted that urea-induced denaturation proceeds through the accumulation of urea at the protein surface and their subsequent interaction. In contrast, it has been suggested that TMAO's protein-stabilizing effects stem from its exclusion from the protein surface, and its ability to deplete urea from protein surfaces; however, these spatial relationships are uncertain. We used neutron diffraction, coupled with structural refinement modeling, to study the spatial associations of TMAO and urea with the tripeptide derivative glycine-proline-glycinamide in aqueous urea, aqueous TMAO, and aqueous urea-TMAO (in the mole ratio 1:2 TMAO:urea). We found that TMAO depleted urea from the peptide's surface and that while TMAO was not excluded from the tripeptide's surface, strong atomic interactions between the peptide and TMAO were limited to hydrogen bond donating peptide groups. We found that the repartition of urea, by TMAO, was associated with preferential TMAO-urea bonding and enhanced urea-water hydrogen bonding, thereby anchoring urea in the bulk solution and depleting urea from the peptide surface.
Cited by 11Open access
Klaus B. Møller, Rossend Rey, Marco Masia et al. · The Journal of Chemical Physics · 2005
The connection between diffusion and solvent exchanges between first and second solvation shells is studied by means of molecular dynamics simulations and analytic calculations, with detailed illustrations for water exchange for the Li(+) and Na(+) ions, and for liquid argon. First, two methods are proposed which allow, by means of simulation, to extract the quantitative speed-up in diffusion induced by the exchange events. Second, it is shown by simple kinematic considerations that the instantaneous velocity of the solute conditions to a considerable extent the character of the exchanges. Analytic formulas are derived which quantitatively estimate this effect, and which are of general applicability to molecular diffusion in any thermal fluid. Despite the simplicity of the kinematic considerations, they are shown to well describe many aspects of solvent exchange/diffusion coupling features for nontrivial systems.
Cited by 46Open access
Taritra Mukherjee (22267842), Benjamin Breitbach (22267845), Moreno Meneghetti (1449013) et al. · Figshare · 2025
We apply Raman solvation shell spectroscopy (or Raman multivariate curve resolution, i.e., Raman-MCR) on aqueous dispersions of various small particles to distinguish the bulk and the solute-correlated spectra. We previously reported the successful application of the technique on a nanoparticle system. Extending that effort, we sought to answer some questions regarding the applicability of the technique to a wider range of particle dispersions. These questions dictate the choice of materials in this work. Using aqueous dispersions of pulsed laser ablated silver and gold nanoparticles, we find that the energy proximity of the surface plasmonic peak of the particle and the laser emission wavelength used for Raman measurements has no qualitative effect on the Raman-MCR spectral outcome. However, it can assist the detection of bulk to interfacial differences by magnifying them. Furthermore, we report successful implementation of the technique on nonmetallic particles (zinc oxide and titanium dioxide) in aqueous dispersions, which alleviates potential concerns if the metallic nature of the dispersed particles was a prerequisite for applicability of the method. A common trend in the results is also observed for the systems we examined. On moving from the bulk to the solute-correlated component, the relative spectral intensities change at the ∼3250, ∼3400, and ∼3610 cm<sup>–1</sup> regions in the water O–H stretching band, observable as a blue shift. This suggests a disruption in the aqueous hydrogen-bonding network within the solvation shell water. Overall, this work demonstrates Raman solvation shell spectroscopy to be a reliable and robust tool to study solvation shells around diverse systems of small particles in dispersions.
Cited by 0Open access