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Rank-dependent orientational relaxation in an ionic liquid: an all-atom simulation study

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Abstract

We have employed all-atom molecular dynamics simulation to investigate the heterogeneity effects on reorientation correlation time in the ionic liquid (IL), 1-butyl-3-methylimidazolium hexafluorophosphate ([Bmim][PF6]), at 298 and 450 K. Our simulated density, radial distribution functions, viscosity, and self-diffusion coefficients compare well with the existing literature data. Even though the room temperature (298 K) simulations could not probe the entire decay of the reorientation correlation function (C l (t)) due to the inherent slow diffusional timescale in this IL and limited computational resources available, the simulated C l (t) at high temperature (450 K) captures the entire decay. The ratio between the simulated reorientation time constants, \( R = \frac{{\int_{0}^{\infty } {{\text{d}}tC_{1} (t )} }}{{\int_{0}^{\infty } {{\text{d}}tC_{2} (t )} }} = \frac{{\left\langle {\tau_{1} } \right\rangle }}{{\left\langle {\tau_{2} } \right\rangle }} \), differs considerably from 3 at 450 K, indicating the presence of significant heterogeneity effects even at this high temperature. This observation corroborates well with the simulated non-Gaussian parameter at this temperature.

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Acknowledgments

We are thankful to Prof. A. P. Lyubartsev, Prof. S. Balasubramanian, Dr. H. K. Kashyap, and Mr. S. Jabes for many helpful discussions. We thank Prof. M. Maroncelli for a critical reading of the manuscript. We thank anonymous reviewers for comments and criticisms which have helped improving the quality of the manuscript. This work is partially supported by the Thematic Unit of Excellence on Computational Materials Science at the S. N. Bose National Centre for Basic Sciences (Project No. SR/NM/NS-29/2011(G)).

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  1. Department of Chemical, Biological and Macromolecular Sciences, S. N. Bose National Centre for Basic Sciences, Block-JD, Sector-III, Salt Lake, Kolkata, 700098, India

    Tamisra Pal & Ranjit Biswas

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  1. Tamisra Pal
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  2. Ranjit Biswas
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Correspondence to Ranjit Biswas.

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Published as part of the special collection of articles derived from the conference: Foundations of Molecular Modeling and Simulation 2012.

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Pal, T., Biswas, R. Rank-dependent orientational relaxation in an ionic liquid: an all-atom simulation study. Theor Chem Acc 132, 1348 (2013). https://doi.org/10.1007/s00214-013-1348-6

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