Hydroxide hydrogen bonding: Probing the solvation structure through ultrafast time domain Raman spectroscopy

Heisler, Ismael A., Mazur, Kamila and Meech, Stephen R. ORCID: https://orcid.org/0000-0001-5561-2782 (2011) Hydroxide hydrogen bonding: Probing the solvation structure through ultrafast time domain Raman spectroscopy. The Journal of Physical Chemistry Letters, 2 (10). pp. 1155-1160. ISSN 1948-7185

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The mechanism of charge transport in aqueous media is critical in molecular, materials, and life sciences. The structure of the solvated hydroxide ion has been an area of some controversy. Polarization-resolved ultrafast time domain polarizability relaxation is used here to resolve the terahertz frequency Raman spectrum of hydroxide solutions. The measurements reveal the totally symmetric hydrogen-bond stretching (HO–···HOH) mode of the solvated hydroxide, permitting an experimental measurement of the bond force constant. The observed polarized Raman spectra are compared with those obtained from DFT calculations performed on HO–(H2O)n clusters. Good agreement between the observed frequency and the polarization dependence is found for the n = 3 or 4 clusters, particularly for those in which the solvating water molecules adopt a planar structure. The frequency of the symmetric stretch increases with concentration, consistent with an effect of ionic strength on either the H-bond or the structure of the cluster.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User: Users 2731 not found.
Date Deposited: 18 Jan 2012 10:26
Last Modified: 17 Jan 2024 01:19
URI: https://ueaeprints.uea.ac.uk/id/eprint/36230
DOI: 10.1021/jz200350q

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