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A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions

Nature Chemistry volume 5, pages 29–35 (2013)Cite this article

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Abstract

In liquid water the transfer of an excess proton between two water molecules occurs through the Zundel cation, H2O···H+···OH2. The proton-transfer mode is the asymmetric stretch of the central O···H+···O moiety, but there is no consensus on its identification in the infrared spectra of acidic aqueous solutions. Also, in experiments with protonated gas-phase water clusters, its position shifts with cluster size, which makes its relationship with solution spectra unclear. Here we introduce a ‘clusters-in-liquid’ approach for calculating the infrared spectrum from any set of charges, even single protons. We apply this procedure to multistate empirical valence-bond trajectories of protonated liquid water and to ab initio molecular dynamics of the protonated water dimer and hexamer in the gas phase. The calculated proton-transfer mode is manifested in both systems as a peak near 1,740 cm−1, in quantitative agreement with a band of similar frequency in the experimental infrared spectrum of protonated water clusters.

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Figure 1: The infrared spectra of protonated gas-phase water clusters, H+(H2O)n.
Figure 2: Calculated ‘clusters-in-liquid’ infrared spectra of H+(H2O)n clusters embedded in room-temperature liquid water.
Figure 3: Our strategy for dividing a trajectory of protonated water into its Eigen and Zundel parts.
Figure 4: Clusters-in-liquid infrared spectra for the Eigen and Zundel clusters in protonated liquid water, showing the peaks assigned to the various classes of protons.
Figure 5: Comparison between the calculated AIMD infrared spectra of Zundel-like gas-phase protonated water clusters (green) and experiments (black).

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Acknowledgements

We are indebted to G. A. Voth for a copy of the MS-EVB3 program and to M. A. Johnson and M. Śmiechowski for experimental data. This research was supported by the US–Israel Binational Science Foundation, grant numbers 2006067 and 2010250. The Fritz Haber Center is supported by the Minerva Gesellschaft für die Forschung, Munich.

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  1. The Fritz Haber Research Center, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem, 91904, Israel

    Waldemar Kulig & Noam Agmon

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  1. Waldemar Kulig
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W.K. performed the calculations, prepared the figures and wrote a first draft of the manuscript. N.A. designed the research, interpreted the data and wrote the article.

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Correspondence to Noam Agmon.

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Kulig, W., Agmon, N. A ‘clusters-in-liquid’ method for calculating infrared spectra identifies the proton-transfer mode in acidic aqueous solutions. Nature Chem 5, 29–35 (2013). https://doi.org/10.1038/nchem.1503

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