Gupta Aditya, Sharma Shobha, Kashyap Hemant K
Department of Chemistry, Indian Institute of Technology Delhi, Hauz Khas, New Delhi 110016, India.
J Chem Phys. 2015 Apr 7;142(13):134503. doi: 10.1063/1.4916308.
This article reports results from the molecular dynamics simulations on the structural arrangement of the ions and molecules in the mixtures of trihexyl(tetradecyl)phosphonium chloride ([P666,14 (+)][Cl(-)]) ionic liquid (IL) and methanol (MeOH) over the entire composition range. Effects of composition on the charge and polarity orderings have been investigated via computation of X-ray scattering structure function, S(q), and by using a partitioning scheme proposed for such multi-component mixtures. Except for the neat methanol liquid, the total S(q) shows two peaks in its intermolecular region for all the mole-fractions. The lowest q peak is dominated primarily by anion-anion, cation-anion, and methanol-anion correlations. Our results signify that the methanol bulk structure, which predominantly has short-distance characteristic correlations and is governed by polar group of methanol, is retained for xIL ≤ 0.1. Then, the mixture goes through gradual structural changes from methanol-like to the IL-like for 0.1 < xIL ≤ 0.7. The dipolar interaction between methanol molecules weakens in this range, and the structural landscape of the mixture is steered by strong ion-ion, anion-methanol, and nonpolar interactions. The IL-like structural arrangement is virtually recovered for xIL > 0.7. At all the compositions studied, while the cation head groups are predominantly solvated by anions and subsequently by methanol molecules, the polar hydroxyl group of methanol is preferentially solvated by the anions. The radial distribution functions of selected pair of atomic species have also confirmed these observations.
