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Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization
Abstract
The solute–solvent interaction of salts has a striking impact on various biological and industrial processes but its mechanism remains yet mysterious despite intensive studies since 1888 when Franz Hofmeister established the salt series. A combination of confocal Raman spectroscopy and contact angle measurements has enabled us to resolve the hydrogen bond relaxation (O:H―O, HB) and the associated charge polarization dynamics at different molecular site because of alkali halides hydration. Results show consistently that salt hydration softens the O:H phonon but stiffens H―O phonon cooperatively. The extent of HB relaxation and polarization is proportional to the electronegativity difference and ionic radius, following the order of Hofmeister series: X (R/η) = I (2.2/2.5) > Br (1.96/2.8) > Cl (1.81/3.0) > F (1.33/4.0) ≈ 0 for anions, and Y(R/η) = Na (0.98/0.9) > K (1.33/0.8) > Rb (1.49/0.8) > Cs (1.65/0.8) for cations. Observations suggest that ions create each an electric field that aligns, stretches, and polarizes water molecules, which relaxes the O:H―O bond cooperatively, depresses the molecular dynamics, and enhances the hydration shell viscosity and the skin stress. Exercises also demonstrate that Raman spectroscopy performs as a powerful tool for probing the molecular‐site‐resolved HB network relaxation dynamics in terms of phonon stiffness, molecular fluctuation dynamics, and phonon abundance transition under external stimulus. Copyright © 2016 John Wiley & Sons, Ltd.
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“The results showed that the ratio decreased in the following order: SO4 2 > Ac > Cl > I , which is in agreement with previous reports [67,68].”
From Effect of Hofmeister Anions on Interfacial Properties of Mica Surface in Concentrated Aqueous Solution (2020) · cites this paper as [67]
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Cited by
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Kan, Y., Yang, Q., Zhang, X., & Zhang, Y. (2020) · Coatings · doi:10.3390/coatings10090872 · Cited by 4
“The results showed that the ratio decreased in the following order: SO42− > Ac− > Cl− > I−, which is in agreement with previous reports [67,68].”
Result
Metadata
- Authors
- Gong, Y., Zhou, Y., Wu, H., Wu, D., Huang, Y., & Sun, C. Q.
- Affiliations
- China Jiliang University (CN)
- Xiangtan University (CN)
- Nanyang Technological University (SG)
- Corresponding author
- Gong, Yinyan
- Venue
- Journal of Raman Spectroscopy
- Publisher
- Wiley
- Published
- 2016-06-14
- Volume
- 47
- Issue
- 11
- Pages
- 1351-1359
- ISSN
- 0377-0486 (ISSN-L)
- 1097-4555
- OpenAlex
- W2435419344
- Cited by
- 40
- References
- 0
- Citations by year
- 2026: 2 · 2025: 2 · 2024: 2 · 2023: 1 · 2022: 4 · 2021: 1 · 2020: 4 · 2019: 9 · 2018: 2 · 2017: 8 · 2016: 4
- FWCI
- 3.63
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of Raman Spectroscopy (publishedVersion)
- Funders
- National Natural Science Foundation of China (21273191, 11502223, 51402277, 51402274)
- Topics
- Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Chemical and Physical Studies
- Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Spectroscopy Techniques in Biomedical and Chemical Research
- Keywords
- water polarization, Hofmeister series, solute-solvent interactions, ionic radius, electronegativity difference, confocal Raman spectroscopy, contact angle
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