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Using FT-IR spectroscopy to measure charge organization in ionic liquids.

ABSTRACT: A major goal in the field of ionic liquids is correlating transport property trends with the underlying liquid structure of the compounds, such as the degree of charge organization among the constituent ions. Traditional techniques for experimentally assessing charge organization are specialized and not readily available for routine measurements. This represents a significant roadblock in elucidating these correlations. We use a combination of transmission and polarized-ATR infrared spectroscopy to measure the degree of charge organization for ionic liquids. The technique is illustrated with a family of 1-alkyl-3-methylimidazolium trifluoromethanesulfonate ionic liquids at 30 °C. As expected, the amount of charge organization decreases as the alkyl side chain is lengthened, highlighting the important role of short-range repulsive interactions in defining quasilattice structure. Inherent limitations of the method are identified and discussed. The quantitative measurements of charge organization are then correlated with trends in the transport properties of the compounds to highlight the relationship between charge and momentum transport and the underlying liquid structure. Most research laboratories possess infrared spectrometers capable of conducting these measurements; thus, the proposed method may represent a cost-effective solution for routinely measuring charge organization in ionic liquids.

SUBMITTER: Burba CM

PROVIDER: S-EPMC3813306 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

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Using FT-IR spectroscopy to measure charge organization in ionic liquids.

Burba Christopher M CM Janzen Jonathan J Butson Eric D ED Coltrain Gage L GL

The journal of physical chemistry. B 20130711 29

A major goal in the field of ionic liquids is correlating transport property trends with the underlying liquid structure of the compounds, such as the degree of charge organization among the constituent ions. Traditional techniques for experimentally assessing charge organization are specialized and not readily available for routine measurements. This represents a significant roadblock in elucidating these correlations. We use a combination of transmission and polarized-ATR infrared spectroscopy ...[more]

PMID: 23781877

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Project description:Charge scaling as an effective solution to the experiment-computation disagreement in molecular modelling of ionic liquids (ILs) could bring the computational results close to the experimental reference for various thermodynamic properties. According to the large-scale benchmark calculations of mass density, solvation, and water-ILs transfer-free energies in our series of papers, the charge-scaling factor of 0.8 serves as a near-optimal option generally applicable to most ILs, although a system-dependent parameter adjustment could be attempted for further improved performance. However, there are situations in which such a charge-scaling treatment would fail. Namely, charge scaling cannot really affect the simulation outcome, or minimally perturbs the results that are still far from the experimental value. In such situations, the vdW radius as an additional adjustable parameter is commonly tuned to minimize the experiment-calculation deviation. In the current work, considering two ILs from the quinuclidinium family, we investigate the impacts of this vdW-scaling treatment on the mass density and the solvation/partition thermodynamics in a fashion similar to our previous charge-scaling works, i.e., scanning the vdW-scaling factor and computing physical properties under these parameter sets. It is observed that the mass density exhibits a linear response to the vdW-scaling factor with slopes close to -1.8 g/mL. By further investigating a set of physiochemically relevant temperatures between 288 K and 348 K, we confirm the robustness of the vdW-scaling treatment in the estimation of bulk properties. The best vdW-scaling parameter for mass density would worsen the computation of solvation/partition thermodynamics, and a marginal decrease in the vdW-scaling factor is considered as an intermediate option balancing the reproductions of bulk properties and solvation thermodynamics. These observations could be understood in a way similar to the charge-scaling situation. i.e., overfitting some properties (e.g., mass density) would degrade the accuracy of the other properties (e.g., solvation free energies). Following this principle, the general guideline for applying this vdW-tuning protocol is by using values between the density-derived choice and the solvation/partition-derived solution. The charge and current vdW scaling treatments cover commonly encountered ILs, completing the protocol for accurate modelling of ILs with fixed-charge force fields.

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Using FT-IR spectroscopy to measure charge organization in ionic liquids.

Publications

Using FT-IR spectroscopy to measure charge organization in ionic liquids.

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