TiCl4 Dissolved in Ionic Liquid Mixtures from Аb Initio Molecular Dynamics Simulations |
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Authors: | Lars Esser Roberto Macchieraldo Roman Elfgen Melanie Sieland Bernd Michael Smarsly Barbara Kirchner |
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Institution: | 1.Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstrasse 4+6, D-53115 Bonn, Germany; (L.E.); (R.M.); (R.E.);2.Institute of Physical Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, D-35392 Giessen, Germany; (M.S.); (B.M.S.) |
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Abstract: | To gain a deeper understanding of the TiCl solvation effects in multi-component ionic liquids, we performed ab initio molecular dynamics simulations of 1-butyl-3-methylimidazolium CCIm], tetrafluoroborate BF], chloride Cl] both with and without water and titanium tetrachloride TiCl. Complex interactions between cations and anions are observed in all investigated systems. By further addition of water and TiCl this complex interaction network is extended. Observations of the radial distribution functions and number integrals show that water and TiCl not only compete with each other to interact mainly with Cl], which strongly influences the cation-BF] interaction, but also interact with each other, which leads to the fact that in certain systems the cation-anion interaction is enhanced. Further investigations of the Voronoi polyhedra analysis have demonstrated that water has a greater impact on the nanosegregated system than TiCl which is also due to the fact of the shear amount of water relative to all other components and its higher mobility compared to TiCl. Overall, the polar network of the IL mixture collapses by including water and TiCl. In the case of Cl] chloride enters the water continuum, while BF] remains largely unaffected, which deeply affects the interaction of the ionic liquid (IL) network. |
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Keywords: | ionic liquids ab initio molecular dynamics simulations TiO2 material synthesis in ionic liquids |
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