Dielectric permittivity of aqueous solutions of electrolytes probed by THz time-domain and FTIR spectroscopy

Ninno, A. De; Nikollari, Ermal; Missori, Mauro; Frezza, Fabrizio

doi:10.1016/j.physleta.2020.126865

Cited by 14 publications

(9 citation statements)

References 42 publications

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“…Usually, high permittivity solvents will see a decrease in the value of e r with the addition of a salt while lower permittivity solvents can see the reverse. The former is thought to be due to an entropic effect of locking solvent dipoles into solvation shells of ions (salt-screening of solvent-solvent correlations), and the latter due to ion pairing and polarisation of the solvent, as proposed by Grzetic et al 288 To illustrate the effect of adjusting the value of the static permittivity on the Debye and Bjerrum lengths, experimental values [289][290][291][292][293][294] were collected and fitted to a functional form provided by Gavish and Promislow 295 (detailed in the ESI †), and the correction is shown in Fig. 16.…”

Section: Sies In Concentrated Electrolytesmentioning

confidence: 99%

See 1 more Smart Citation

Understanding specific ion effects and the Hofmeister series

Gregory

Elliott

Robertson

et al. 2022

Phys. Chem. Chem. Phys.

189

111

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Section: Sies In Concentrated Electrolytesmentioning

confidence: 99%

“…To illustrate the effect of adjusting the value of the static permittivity on the Debye and Bjerrum lengths, experimental values 289–294 were collected and fitted to a functional form provided by Gavish and Promislow 295 (detailed in the ESI†), and the correction is shown in Fig. 16.…”

Section: Sies In Concentrated Electrolytesmentioning

confidence: 99%

Understanding specific ion effects and the Hofmeister series

Gregory

Elliott

Robertson

et al. 2022

Phys. Chem. Chem. Phys.

189

111

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show abstract

“…Water is the most important liquid in biological media. The basic objective of chemistry and biology is to understand the molecular structure of liquid water, particularly the hydrogen bond between water molecules [11] . The biochemical interaction between liquid water and biomolecules constitutes the biological environment and influences the activity of the biomolecules.…”

Section: Resultsmentioning

confidence: 99%

Terahertz spectra of electrolyte solutions under applied electric and magnetic fields

Shen¹,

Liu²,

Ding³

et al. 2022

J. Eur. Opt. Society-Rapid Publ.

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Most biomolecules require an aqueous environment to fully exert their biological activity. However, the rotation mode, vibration mode, and energy associated with the hydrogen bonding network of water are in the terahertz band, resulting in strong absorption. Therefore, it is difficult to detect liquid biological samples using the terahertz technology. Here, a high-transmittance double-layer microfluidic chip was prepared using a cycloolefin copolymer material with high transmittance of terahertz waves. Combined with terahertz time-domain spectroscopy, the terahertz spectral characteristics of deionized water, NaCl, NaCO3, and CH3COONa solutions were studied. The changes in the terahertz transmission intensity of these electrolyte solutions under constant electric and magnetic fields were measured. The results show that the terahertz spectra of different sodium salt solutions with the same concentration of 0.9 mol/l are different. Furthermore, the terahertz absorption coefficients of the different electrolyte solutions gradually decrease with the increase of their residence time under the electric field, which is contrary to the results obtained under the external magnetic field. This study provides a new idea for the detection of sodium salt solution and lays a foundation for the development of THz technology.

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“…It matches some simulation data as well as several consequences of the nonlocal dielectric response of water. , This concept has been discussed in detail in ref in the context of the interplay between temporal and spatial correlations of polarization fluctuations. It is tempting to relate this splitting of the polarization density with the well-known attempts to fit the Debye spectrum of the frequency dependent dielectric permittivity of water with two different relaxation times, − one fast and one slow, often associated with librations of individual molecules and reorientations of their larger clusters, respectively. But this does not mean that water should be literally considered as a coupled system of two liquids, each with their own relaxation processes, although new arguments to validate such a picture have been raised , in the context of recently discussed “low” and “high” density clusters in water.…”

Section: Phenomenological Theory For Pure Watermentioning

confidence: 99%

The Dramatic Effect of Water Structure on Hydration Forces and the Electrical Double Layer

2023

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Forces between hydrophilic surfaces mediated by water are important in various systems from lipid membranes and solid surfaces to colloids and macromolecules, first discovered as a significant addition to DLVO forces at the nanoscale. These “hydration forces” have been studied in great detail experimentally using osmotic stress measurements, surface force apparatus, and AFM, and they have also been the subject of multiple theories and simulations. One spectacular feature observed in experimental and simulation studies was the nonmonotonic, oscillatory decay in the forces between atomically smooth surfaces. Forces between “rougher” surfaces exhibit only quasi-exponential, monotonic decay. Here we revisit this hydration force problem by exploring the consequences of an extended phenomenological Landau–Ginzburg approach that describes nonlocal correlations in water, linking them with the key features of the wave-number k-dependent nonlocal dielectric function of water. With corresponding boundary conditions, this theory predicts the observed oscillatory decay in hydration force between ideally flat surfaces, the oscillatory mode disappearing with just a tiny roughness of the surfaces (of mean height ca. of the size of a water molecule). This study also brings an important side message. Explanation of these observations appears only possible under an assumption of two modes of polarization in water, consistent with the behavior of the response function, i.e., Lorentzian at small k and resonance-like at higher k. This resolves the “force oscillation–non-oscillation” paradigm, which is a strong, although indirect indication of the existence of these two modes. We also consider other important subjects, such as how the distribution of ions near a charged surface reacts to the propensity for overscreening oscillations due to polarized water. This is important not only for the interactions between charged surfaces but also for the fundamental understanding of the structure of the electrical double layer at electrochemical interfaces. We show that even in dilute electrolytes, the distribution of ions in the vicinity of the polarized interface follows, although not literally, preferential positions corresponding to the potential wells caused by “resonance” water layering. For a sharp interface, the theory predicts that the decaying spatial oscillation profiles extend over a 1 to 2 nm distance from the interface. With the smearing of the interface and the corresponding suppression of the resonance water layering, oscillations in the spatial distribution of ions subside, resulting in a familiar Gouy–Chapman–Stern picture. At longer distances from the interface, whether smeared or not, the ion distribution profiles become Gouy–Chapman-like. The effect of the boundary conditions on water polarization at the interface goes beyond a trivial shift of the potential of zero charge. We show that they can dramatically affect the ion distribution near the charged surface. Last, but not least, we study how the interfacial water layerin...

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Dielectric permittivity of aqueous solutions of electrolytes probed by THz time-domain and FTIR spectroscopy

Cited by 14 publications

References 42 publications

Understanding specific ion effects and the Hofmeister series

Understanding specific ion effects and the Hofmeister series

Terahertz spectra of electrolyte solutions under applied electric and magnetic fields

The Dramatic Effect of Water Structure on Hydration Forces and the Electrical Double Layer

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