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Properties of hydrogen bonds in the protic ionic liquid ethylammonium nitrate

DFT versus DFTB molecular dynamics

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Abstract

Comparative molecular dynamics simulations of a hexamer cluster of the protic ionic liquid ethylammonium nitrate are performed using density functional theory and density functional-based tight-binding (DFTB) methods. The focus is on assessing the performance of the DFTB approach to describe the dynamics and infrared spectroscopic signatures of hydrogen bonding between the ions. Average geometries and geometric correlations are found to be rather similar. The same holds true for the far-infrared spectral region. Differences are more pronounced for the NH- and CH-stretching bands, where DFTB predicts a broader intensity distribution. DFTB completely fails to describe the fingerprint range shaped by nitrate anion vibrations. Finally, charge fluctuations within the H bonds are characterized yielding moderate dependencies on geometry. On the basis of these results, DFTB is recommended for the simulation of H bond properties of this type of ionic liquid.

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Acknowledgements

The authors thank the Deutsche Forschungsgemeinschaft (DFG) for financial support through the SFB 652 and A. Wulf for supplying the experimental FIR spectra.

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Authors and Affiliations

  1. Institut für Physik, Universität Rostock, Albert-Einstein-Str. 23-24, 18059, Rostock, Germany

    Tobias Zentel & Oliver Kühn

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  1. Tobias Zentel
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  2. Oliver Kühn
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Correspondence to Oliver Kühn.

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Zentel, T., Kühn, O. Properties of hydrogen bonds in the protic ionic liquid ethylammonium nitrate. Theor Chem Acc 136, 87 (2017). https://doi.org/10.1007/s00214-017-2119-6

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