Communication: Nanoscale structure of tetradecyltrihexylphosphonium based ionic liquids

• Published in: The Journal of chemical physics 2016-03, Vol.144 (12), p.121102-121102
• Main Authors: Hettige, Jeevapani J., Araque, Juan C., Kashyap, Hemant K., Margulis, Claudio J.
• Format: Article
• Language: English
• Subjects: AMIDES; ANIONS; Cations; FLUORINE COMPOUNDS; INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; Ionic liquids; Ions; MOLTEN SALTS; Periodic variations; PHOSPHORUS COMPOUNDS; Physics; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0400-1000 K; X-RAY DIFFRACTION
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.4944678

In a recent communication [J. J. Hettige et al., J. Chem. Phys. 140, 111102 (2014)], we investigated the anomalous temperature dependence of the X-ray first sharp diffraction peak (or prepeak) in the tetradecyltrihexylphosphonium bis(trifluoromethylsulfonyl)-amide ionic liquid. Contrary to what was expected and often observed, the first sharp diffraction peak in this system was shown to increase in intensity with increasing temperature. This implies higher intermediate-range periodicity at a higher temperature. Is this counter-intuitive behavior specific to the combination of cation and anion? The current work analyzes the structural behavior of the same cation coupled with six different anions ranging from the small and spherically symmetric Cl− to the more structurally complex and charge-diffuse NTf2 −. In all cases, the same temperature behavior trend for the prepeak is observed independent of anionic nature. We will show that the intensity increase in the prepeak region is associated with the structural behavior of charged liquid subcomponents. Instead, upon a temperature increase, the apolar subcomponents contribute to what would be an expected decrease of prepeak intensity.