October 28, 2021

Hosein Eslami

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Faculty: Faculty of Nano and Biotechnology

Research

Title Molecular Dynamics Simulation of the Ionic Liquid 1- n - Butyl-3-Methylimidazolium Methylsulfate [Bmim][MeSO 4 ]: Interfacial Properties at the Silica and Vacuum Interfaces
Type Article
Keywords
Journal CHEMPHYSCHEM
DOI
Researchers Nargess Mehdipour (Second researcher) , Hosein Eslami (Third researcher)

Abstract

Molecular dynamics simulations are done to investigate the structure and dynamics of a thin [Bmim][MeO 4 ] film in contact with a hydroxylated silica surface on one side and with vacuum on the other. An examination of the microscopic structure of ionic liquid (IL) film shows that strong layered anionic/cationic structures are formed at both interfaces. At the silica interface, the imidazolium rings are closer to the silica surface (compared to anions) and are coplanar with it. At the vacuum interface, the charged imidazolium ring more concentrates in the interior of the film, but the butyl side chain stretches out toward the vacuum interface. While there exists an excess concentration of the cations at the silica interface, at the vacuum interface an excess concentration of anions (dissolved in the butyl chain) is found. The influence of the interface on the dynamical proper- ties is shown to depend on their time scales. A short-time dynamical property, such as hydrogen bond formation is not noticeably perturbed at the interface. In contrary, long-time properties such as ion-pair formation/rupture and translation of ions across the film are largely decelerated at the silica interface but are accelerate at the vacuum interface. Our findings indicate that the structural relaxation time of ion-pairs, is comparable to diffusion time scale in the IL film. Therefore, ion- pairs are not stable species; the IL is composed of short-lived ion-pairs and freely diffusing ions. However, the structural relaxation times of ion-pairs is still long enough (comparable to the time scale of diffusion) to conclude that correlated motions of counterions influence the macroscopic properties of IL, such as diffusion and ionic conductivity. In this respect, we have shown that correcting the Nernst-Einstein equation for the joint translation of ion-pairs considerably improves the accuracy of calculated ionic conductivities.