TiCl4 Dissolved in Ionic Liquid Mixtures from Ab Initio Molecular Dynamics Simulations

L Esser and R Macchieraldo and R Elfgen and M Sieland and BM Smarsly and B Kirchner, MOLECULES, 26, 79 (2021).

DOI: 10.3390/molecules26010079

To gain a deeper understanding of the TiCl4 solvation effects in multi- component ionic liquids, we performed ab initio molecular dynamics simulations of 1-butyl-3-methylimidazolium C(4)C(1)Im(+), tetrafluoroborate BF4(-), chloride Cl(-) both with and without water and titanium tetrachloride TiCl4. Complex interactions between cations and anions are observed in all investigated systems. By further addition of water and TiCl4 this complex interaction network is extended. Observations of the radial distribution functions and number integrals show that water and TiCl4 not only compete with each other to interact mainly with Cl-, which strongly influences the cation-BF4(-) 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 TiCl4 which is also due to the fact of the shear amount of water relative to all other components and its higher mobility compared to TiCl4. Overall, the polar network of the IL mixture collapses by including water and TiCl4. In the case of Cl- chloride enters the water continuum, while BF4(-) remains largely unaffected, which deeply affects the interaction of the ionic liquid (IL) network.

Return to Publications page