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Prediction of ionic conductivity from adiabatic heating in non-equilibrium molecular dynamics on various test systems

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Abstract

Context

The evaluation of ionic conductivity through atomistic modeling typically involves calculating diffusion coefficients, which often necessitates simulations spanning several hundreds of nanoseconds. This study introduces a less computationally demanding approach based on non-equilibrium molecular dynamics applicable to a wide range of systems.

Method

Ionic conductivity is determined by evaluating the Joule heating effect recorded during non-equilibrium molecular dynamics (NEMD) simulations. These simulations which involve applying a uniform electric field using classical force fields in LAMMPS are conducted within the MedeA software environment. The conductivity value for a specific temperature can thus be obtained from a single simulation together with an estimation of the associated uncertainty. Guidelines for selecting NEMD parameters such as electric field intensity and initial temperature are proposed to satisfy linear irreversible transport.

Results

The protocol presented in this study is applied to four different types of systems, namely, (i) molten NaCl, (ii) NaCl and LiCl aqueous solutions, (iii) solution of ionic liquid with two solvents, and (iv) NaX zeolites in the anhydrous and hydrated states. The main advantages of the proposed protocol are simplicity of implementation (eliminating the need to store individual ion trajectories), reliability (low electric field, linear response, no perturbation of the equations of motion by a thermostat), and a wide range of applications. The estimated contribution of field-induced drift motion of ions to kinetic energy appears very low, justifying the use of standard kinetic energy in the method. For each system, the reported influence of temperature, ion concentration, solvent nature, or hydration is correctly predicted.

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Data availability

The datasets generated during and/or analyzed during the current study are available from the corresponding author upon reasonable request.

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Acknowledgements

The author thanks Stephane Tesson, Marianna Yiannourakou, Xavier Rozanska, and Benoit Leblanc for their help and advice in the implementation of NEMD with the ClayFF forcefield. Fruitful discussions with Erich Wimmer, Alexander Mavromaras, Guillaume Galliero, Arthur France-Lanord, Véronique Lachet, René Windiks, and Shubham Pandey are gratefully acknowledged. The work was realized between January 2018 and January 2023 with the support of Materials Design, Inc.

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  1. Materials Design SA, 42 Av. Verdier, 92120, Montrouge, France

    Philippe Ungerer & Benoit Minisini

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  1. Philippe Ungerer
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Contributions

All authors contributed to the study’s conception and design. The method was established, and tests were performed on molten NaCl, NaCl, and LiCl aqueous solutions and NaX zeolites systems by Philippe Ungerer. Tests on ionic liquids + solvents were performed by Benoit Minisini. The first draft of the manuscript was written by Philippe Ungerer, and both authors commented on previous versions of the manuscript. Both authors read and approved the final manuscript.

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Correspondence to Benoit Minisini.

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Ungerer, P., Minisini, B. Prediction of ionic conductivity from adiabatic heating in non-equilibrium molecular dynamics on various test systems. J Mol Model 29, 234 (2023). https://doi.org/10.1007/s00894-023-05640-2

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