Tricationic Ionic Liquids: Structural and Dynamical Properties via Molecular Dynamics Simulations

Three imidazolium-based linear tricationic ionic liquids (LTILs) have been simulated to study their structural and dynamical properties and obtain a fundamental understanding of the molecular basis of the microscopic and macroscopic properties of their bulk liquid phase. The effects of temperature and alkyl chain length on the physiochemical, transport, and structural properties of these LTILs have been investigated. A nonpolarizable all-atom force field, which is a refined version of the Canongia Lopes and Paudua force field, was adopted for the simulations. Densities, mean square displacements, self-diffusivities, viscosities, electrical conductivities, and transference numbers have been presented for various ions from MD simulations. The detailed microscopic structures have been discussed in terms of radial distribution functions and spatial distribution functions. The results show that, similar to that in monocationic and dicationic ILs (MILs and DILs, respectively), the anions are mainly organized around the imidazolium rings. The diffusion coefficients of the studied LTILs are smaller than those of both MILs and DILs, with comparable viscosities. Unlike those of MILs and DILs, the diffusion coefficients of the cations and anions of the studied LTILs increase with an increase in the length of the alkyl chain between the rings for LTIL-1 and LTIL-2 but then decrease for LTIL-3, which is in a good agreement with the trend of viscosity data. The calculated transference numbers show that, similar to that in MILs and DILs, cations have a major role in carrying electric current in LTILs, but this role increases from MILs to LTILs

Evaluating the Effects of Geometry and Charge Flux in Force Field Modeling

We apply a model for analyzing the importance of conformational charge flux to 11 molecules with the R–(CH₂)_<i>n</i>–R structure (R = Cl, F, OH, SH, COOH, CONH₂, and NH₂ and <i>n</i> = 4–6). Atomic charges were obtained by fitting to results from density functional theory calculations using the HLY procedure, and their geometry dependence is decomposed into contributions from changes in bond lengths, bond angles, and torsional angles. The torsional degrees of freedom are the main contribution to the conformational dependence of atomic charges and molecular dipole moments, but indirect effects due to changes in bond distances and angles account for ∼15% of the variations. While the magnitude of charge flux and geometry effects have been found to be independent of the number of internal degrees of freedom, the nature of the R- group has a moderate influence. The indirect effects are comparable for all of the R-groups and are approximately one-half the magnitude of the corresponding effects in peptide models. However, the magnitudes are different, yet the relative importance of geometry and charge flux effects are completely similar to those of the peptide models, which suggests that modeling the charge flux effects for changes in bond lengths, bond angles, and torsional angles should be considered for developing improved force fields

Evaluating the Effects of Geometry and Charge Flux in Force Field Modeling

We apply a model for analyzing the importance of conformational charge flux to 11 molecules with the R–(CH₂)_<i>n</i>–R structure (R = Cl, F, OH, SH, COOH, CONH₂, and NH₂ and <i>n</i> = 4–6). Atomic charges were obtained by fitting to results from density functional theory calculations using the HLY procedure, and their geometry dependence is decomposed into contributions from changes in bond lengths, bond angles, and torsional angles. The torsional degrees of freedom are the main contribution to the conformational dependence of atomic charges and molecular dipole moments, but indirect effects due to changes in bond distances and angles account for ∼15% of the variations. While the magnitude of charge flux and geometry effects have been found to be independent of the number of internal degrees of freedom, the nature of the R- group has a moderate influence. The indirect effects are comparable for all of the R-groups and are approximately one-half the magnitude of the corresponding effects in peptide models. However, the magnitudes are different, yet the relative importance of geometry and charge flux effects are completely similar to those of the peptide models, which suggests that modeling the charge flux effects for changes in bond lengths, bond angles, and torsional angles should be considered for developing improved force fields

Probing the Importance of Charge Flux in Force Field Modeling

We analyze the conformational dependence of atomic charges and molecular dipole moments for a selection of ∼900 conformations of peptide models of the 20 neutral amino acids. Based on a set of reference density functional theory calculations, we partition the changes into effects due to changes in bond distances, bond angles, and torsional angles and into geometry and charge flux contributions. This allows an assessment of the limitations of fixed charge force fields and indications for how to design improved force fields. The torsional degrees of freedom are the main contribution to conformational changes of atomic charges and molecular dipole moments, but indirect effects due to change in bond distances and angles account for ∼25% of the variation. Charge flux effects dominate for changes in bond distances and are also the main component of the variation in bond angles, while they are ∼25% compared to the geometry variations for torsional degrees of freedom. The geometry and charge flux contributions to some extent produce compensating effects