Abstract
The structural and dynamical properties of water are known to be affected by ion solvation. However, a consistent molecular picture that describes how and to what extent ions perturb the water structure is still missing. Here we apply 2D Raman–terahertz spectroscopy to investigate the impact of monatomic cations on the relaxation dynamics of the hydrogen-bond network in aqueous salt solutions. The inherent ability of multidimensional spectroscopy to deconvolute heterogeneous relaxation dynamics is used to reveal the correlation between the inhomogeneity of the collective intermolecular hydrogen-bond modes and the viscosity of a salt solution. Specifically, we demonstrate that the relaxation time along the echo direction t1 = t2 correlates with the capability of a given cation to ‘structure’ water. Moreover, we provide evidence that the echo originates from the water–water modes, and not the water–cation modes, which implies that cations can structure the hydrogen-bond network to a certain extent.
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Acknowledgements
We thank P. J. M. Johnson for many insightful discussions. The work has been supported by the Swiss National Science Foundation (SNF) through the NCCR MUST.
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A.S., J.S and P.H. conceived and designed the experiments. A.S. and S.A. performed the experiments. A.S analysed the data. A.S. and P.H. co-wrote the paper. All the authors discussed the results and commented on the manuscript.
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Shalit, A., Ahmed, S., Savolainen, J. et al. Terahertz echoes reveal the inhomogeneity of aqueous salt solutions. Nature Chem 9, 273–278 (2017). https://doi.org/10.1038/nchem.2642
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DOI: https://doi.org/10.1038/nchem.2642
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