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Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization

Gong, Yinyan, Zhou, Yong, Wu, Huacheng, Wu, Danping, Huang, Yongli, Sun, Chang Q.·2016·Journal of Raman Spectroscopy
DOI 10.1002/jrs.4963
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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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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
ORCID
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
DOI
10.1002/jrs.4963
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
Licence
onlinelibrary.wiley.com/termsAndConditions#vor (vor)
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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CoChat. (2026). Citation check: Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization. https://app.cochat.ai/papers/10.1002/jrs.4963
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Gong, Y., Zhou, Y., Wu, H., Wu, D., Huang, Y., & Sun, C. Q. (2016). Raman spectroscopy of alkali halide hydration: hydrogen bond relaxation and polarization. Journal of Raman Spectroscopy. https://doi.org/10.1002/jrs.4963