Molecular Dynamic Simulations and Vibrational Analysis of an Ionic Liquid Analogue

• Published in: The journal of physical chemistry. B 2013-09, Vol.117 (35), p.10250-10260
• Main Authors: Perkins, Sasha L, Painter, Paul, Colina, Coray M
• Format: Article
• Language: English
• Subjects: Anions; Atomic and molecular physics; Band spectra; Chlorides; Eutectics; Exact sciences and technology; Infrared radiation; Molecular properties and interactions with photons; Physics; Properties of molecules and molecular ions; Simulation; Spectra; Ureas
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/jp404619x

Deep eutectic solvents, considered ionic liquid (IL) analogues, show promise for many material science and engineering applications over typical ILs because they are readily available and relatively inexpensive. Atomistic molecular dynamics simulations have been performed over a range of temperatures on one eutectic mixture, 1:2 choline chloride/urea, using different force field modifications. Good agreement was achieved between simulated density, volume expansion coefficient, heat capacity, and diffusion coefficients and experimental values in order to validate the best performing force field. Atom–atom and center-of-mass radial distribution functions are discussed in order to understand the atomistic interactions involved in this eutectic mixture. Experimental infrared (IR) spectra are also reported for choline chloride–urea mixtures, and band assignments are discussed. The distribution of hydrogen-bond interactions from molecular simulations is correlated to curve-resolved bands from the IR spectra. This work suggests that there is a strong interaction between the NH2 of urea and the chlorine anion where the system wants to maximize the number of hydrogen bonds to the anion. Additionally, the disappearance of free carbonyl groups upon increasing concentrations of urea suggests that at low urea concentrations, urea will preferentially interact with the anion through the NH2 groups. As this concentration increases, the complex remains but with additional interactions that remove the free carbonyl band from the spectra. The results from both molecular simulations and experimental IR spectroscopy support the idea that key interactions between the moieties in the eutectic mixture interrupt the main interactions within the parent substances and are responsible for the decrease in freezing point.