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J Phys Chem B. 2016 Nov 17;120(45):11790-11799. Epub 2016 Nov 7.

Structure and Dynamics of Ionic Liquid [MMIM][Br] Confined in Hydrophobic and Hydrophilic Porous Matrices: A Molecular Dynamics Simulation Study.

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Department of Chemical Sciences, Indian Institute of Science Education and Research Kolkata , Mohanpur 741246, India.


The effects of confinement on the structural and dynamical properties of the ionic liquid (IL) 1,3-dimethylimidazolium bromide ([MMIM][Br]) have been investigated by molecular dynamics simulations. We used zeolite faujasite (NaY) as a hydrophilic confinement and dealuminated faujasite (DAY) as a hydrophobic confinement. The presence of an extra framework cation, [Na+], in NaY makes the host hydrophilic, whereas DAY, with no extra framework cation, is hydrophobic. Although both NaY and DAY have almost similar structures, the IL showed markedly different structural and dynamical properties in these confinements and in bulk. In the confinements, the cation-cation radial distribution function, which strongly depends on temperature, exhibits a layer-like structure, whereas in bulk, it shows a liquid-like structure that hardly depends on temperature. Although the interaction between [MMIM]+ and Br- in DAY is stronger than that in both NaY and bulk, the strength of the interaction between them is almost invariant with temperature. Both [MMIM]+ and Br- strongly interact with Na+ of the host, and their interaction strongly depends on temperature, whereas the interaction of the IL with Si and O is very weak and invariant with temperature. In bulk, the self-diffusion coefficient, [D], of both [MMIM]+ and Br- increases exponentially with temperature, and the D of the cation is slightly higher than that of the anion at all studied temperatures, whereas in the confinements, [MMIM]+ moves much faster than Br-. For example, in the hydrophilic confinement, the D of the cation is 20-30 times higher than that of the anion. The D of both the ions decreases significantly in the confinements as compared to that in bulk. During diffusion, [MMIM]+ diffuses closer to the inner surface in the hydrophilic confinement than that in the hydrophobic confinement. The diffusion pathway imperceptibly depends on temperature but strongly depends on the nature of the confinement. The self part of the time-dependent van Hoove correlation function of [MMIM]+ in the hydrophilic confinement shows a larger deviation from its Gaussian form than that in the hydrophobic confinement at all temperatures, indicating that the long-time dynamics of [MMIM]+ in NaY is more heterogeneous than that in DAY. Although the orientational relaxation time scales of [MMIM]+ in the confinements significantly slowed as compared to those in bulk, confinement does not affect the librational motion of the collective hydrogen-bond network present in the IL.


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