Theoretical Chemistry Accounts

, 132:1348

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

Regular Article

DOI: 10.1007/s00214-013-1348-6

Cite this article as:
Pal, T. & Biswas, R. Theor Chem Acc (2013) 132: 1348. doi:10.1007/s00214-013-1348-6
Part of the following topical collections:
  1. Foundations of Molecular Modeling and Simulation 2012 Collection


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 (Cl(t)) due to the inherent slow diffusional timescale in this IL and limited computational resources available, the simulated Cl(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.


Ionic liquidSimulationOrientational relaxationRank dependence

Supplementary material

214_2013_1348_MOESM1_ESM.doc (232 kb)
Supplementary material 1 (DOC 232 kb)

Copyright information

© Springer-Verlag Berlin Heidelberg 2013

Authors and Affiliations

  1. 1.Department of Chemical, Biological and Macromolecular SciencesS. N. Bose National Centre for Basic SciencesKolkataIndia