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Molecular dynamics simulation study of NH4+ and NH2− in liquid ammonia: interaction potentials, structural and dynamical properties

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Abstract

We provide tailor-made GAFF2-type interaction potentials for modeling ammonium and amide ions in ammonia. Based on harmonic approximation of intra-molecular bond stretching and bending, our force fields nicely reproduce the vibrational modes of NH4+ and NH2−, respectively. Moreover, quantum calculations of pair-wise NH4+/NH2−–NH3 interactions were used for inter-molecular force field parameterization, while (NH3)n, [(NH4)(NH3)n]+, and [(NH2)(NH3)n]− complexes with n > 2, respectively, were reserved for benchmarking in terms of both structure and formation energy. Despite the limited reliability of molecular mechanics models for describing dimer complexes (n = 1), we find that GAFF2 reasonably reproduces [(NH4)(NH3)n]+ species for n = 2–4. For the assessment of [(NH2)(NH3)n]− complexes with n = 2–4, we however suggest the introduction of specific van der Waals parameters for amide-ammonia interactions. The application of the (extended) GAFF2 models is demonstrated for the study of ammonium and amide solvation in liquid ammonia at 240 K and 1 atm, respectively. On this basis, we suggest the applicability of our model for both gas phase and liquid states of ammonia.

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All data is reported within the manuscript. Generally available software was applied as specified.

The authors declare no competing interests.

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Acknowledgments

T. Wonglakhon gratefully acknowledges support from the Royal Thai Government through the Development and Promotion of Science and Technology (DPST) Project.

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Authors and Affiliations

  1. Lehrstuhl für Theoretische Chemie / Computer Chemie Centrum, Friedrich-Alexander Universität Erlangen-Nürnberg, Nägelsbachstraße 25, 91052, Erlangen, Germany

    Tanakorn Wonglakhon & Dirk Zahn

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  1. Tanakorn Wonglakhon
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  2. Dirk Zahn
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T. Wonglakhon performed the simulations and analyzed the results; T. Wonglakhon and D. Zahn planned the study and wrote the manuscript.

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Correspondence to Dirk Zahn.

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Wonglakhon, T., Zahn, D. Molecular dynamics simulation study of NH4+ and NH2− in liquid ammonia: interaction potentials, structural and dynamical properties. J Mol Model 28, 127 (2022). https://doi.org/10.1007/s00894-022-05110-1

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  • DOI: https://doi.org/10.1007/s00894-022-05110-1

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