Molecular Dynamics Simulation Study of the Far-Infrared Spectrum of a Deep Eutectic Solvent

GSA Reis and RMD Souza and MCC Ribeiro, JOURNAL OF PHYSICAL CHEMISTRY B, 126, 5695-5705 (2022).

DOI: 10.1021/acs.jpcb.2c03277

Deep eutectic solvents (DESs) are similar to ionic liquids (IL) in terms of physicochemical properties and technical uses. In ILs, far-infrared (FIR) spectroscopy has been utilized to reveal ionic interactions and even to produce a signature of the strengthening of the cation-anion hydrogen bond. However, for the situation of the DES, where the mixing of a salt and a molecular species makes the interplay between multiple intermolecular interactions even more complex, a full investigation of FIR spectra is still absent. In this work, the FIR spectrum of the DES, often referred to as ethaline, which is a 1:2 mixture of choline chloride and ethylene glycol, is calculated using classical molecular dynamics (MD) simulations and compared to experimental data. To explore the induced dipole effect on the computed FIR spectrum, MD simulations were run with both nonpolarizable and polarizable models. The calculation satisfactorily reproduces the position of the peak at similar to 110 cm(-1) and the bandwidth seen in the experimental FIR spectrum of ethaline. The MD simulations show that the charge current is the most important contributor to the FIR spectrum, but the cross- correlation between the charge current and dipole reorientation also plays a role in the polarizable model. The dynamics of the chloride- ethylene glycol correlation span a wide frequency range, with a maximum at similar to 150 cm(-1), but it participates as a direct mechanism only in the charge current-dipole reorientation cross-term. Anion correlations, whose dynamics are regulated via correlation with both ethylene glycol and choline, make the most significant contribution to the charge current mechanism. The MD simulations were also utilized to investigate the effect on the FIR spectrum of adding water to the DES and switching to a 1:1 composition.

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