NDLI: Vibrational probing of the hydrogen-bond structure and dynamics of water in aqueous NaPF<sub>6</sub> solutions

Content Provider	Royal Society of Chemistry (RSC)
Author	Lee, Chiho Nam, Dayoung Park, Sungnam
Copyright Year	2015
Abstract	Direct measurements of the individual dynamics of water in bulk and ionic hydration shells in aqueous ionic solutions are quite experimentally challenging because the different subsets of water in bulk and ionic hydration shells are not spectrally well-resolved in most aqueous ionic solutions. In contrast, the different subsets of water in the bulk, cationic hydration shell, and anionic hydration shell in aqueous NaPF6 solutions were found to be spectrally well distinct. Such spectral features allowed us to study the individual dynamics of the different subsets of water in aqueous NaPF6 solutions. In this work, we studied the hydrogen-bond (H-bond) structure and dynamics of water in aqueous NaPF6 solutions at different NaPF6 concentrations by FTIR, Raman, and IR pump–probe spectroscopy. Three different subsets of water in the bulk, cationic hydration shell, and anionic hydration shell were found to have their own characteristic hydroxyl stretch peaks (eigen spectra) in FTIR and Raman spectra and have unique vibrational lifetimes independent of NaPF6 concentration. However, the orientational relaxation dynamics, r(t), were not able to be separately measured for three different subsets of water. The overall orientational relaxation times were found to be linearly dependent on the solution viscosity and were reasonably well described by the Debye–Stokes–Einstein equation. Finally, the frequency-dependent transition dipole moments of the hydroxyl (–OD) stretch vibration obtained in neat water and aqueous 3.0 M NaPF6 solution were compared and found to be dependent on the nature of H-bonds.
Starting Page	3520
Ending Page	3527
Page Count	8
File Format	HTM / HTML PDF
ISSN	11440546
Volume Number	39
Issue Number	5
Journal	New Journal of Chemistry
DOI	10.1039/c5nj00160a
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Einstein Viscosity Spectroscopy Hydroxy group Stokes FTIR Dipole Raman
Content Type	Text
Resource Type	Article
Subject	Chemistry Materials Chemistry Catalysis

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