Identification of Multiple Water-Iodide Species in Concentrated NaI Solutions Based on the Raman Bending Vibration of Water

The Journal of Physical Chemistry. a
Matthieu BesemerHenk-Jan van Manen

Abstract

The influence of aqueous electrolytes on the water bending vibration was studied with Raman spectroscopy. For all salts investigated (NaI, NaBr, NaCl, and NaSCN), we observed a nonlinear intensity increase of the water bending vibration with increasing concentration. Different lasers and a tunable frequency-doubled optical parametric oscillator system were used to achieve excitation wavelengths between 785 and 374 nm. Focusing on NaI solutions, the relative enhancement of the water bending vibration was found to increase strongly with excitation photon energy, in line with a preresonance effect from the iodide-water charge-transfer transition. We used multivariate curve resolution (MCR) to decompose the measured Raman spectra of NaI solutions into three interconverting spectral components assigned to bulk water and water molecules interacting with one (X···H-O-H···O) and two (X···H-O-H···X) iodide ions (X = I(-)). The Raman spectrum of solid sodium iodide dihydrate supports the assignment of the latter. Using the MCR results, relative Raman scattering cross sections of 4.0 ± 0.6 and 14.0 ± 0.1 were calculated for the mono- and di-iodide species, respectively (compared to that of bulk water set to unity). In addition, it was fou...Continue Reading

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Citations

Oct 21, 2016·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Chuanyu YanTiancheng Mu
Jan 8, 2021·International Journal of Biological Macromolecules·Zhenquan YeChunyan Yan
May 18, 2021·The Analyst·Henk-Jan van ManenJeroen J Jansen
Dec 7, 2018·The Journal of Physical Chemistry. B·Nicholas H C LewisAndrei Tokmakoff

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