Terahertz dynamics of ionic liquids from a combined dielectric relaxation, terahertz, and optical Kerr effect study: evidence for mesoscopic aggregation

David A. Turton, Johannes Hunger, Alexander Stoppa, Glenn Hefter, Andreas Thoman, Markus Walther, Richard Buchner, Klaas Wynne, LP Sadwick (Editor), CMM OSullivan (Editor)

Research output: Contribution to conferencePaper

2 Citations (Scopus)

Abstract

To exploit the great potential of room-temperature ionic liquids (RTILs) as solvents that offer both low environmental impact and product selectivity, an understanding of the liquid structure, the microscopic dynamics, and the way in which the pertinent macroscopic properties, such as viscosity, thermal conductivity, ionic diffusion, and solvation dynamics depend on these properties, is essential. We have measured the intermolecular dynamics of the 1,3-dialkylimidazolium-based RTILs [emim][BF4], [emim][DCA], and [bmim][DCA], at 25 degrees C from below 1 GHz to 10 THz by ultrafast optical Kerr effect (OKE) spectroscopy and dielectric relaxation spectroscopy (DRS) augmented by time-domain terahertz and far-infrared FTIR spectroscopy. This concerted approach allows a more detailed analysis to be made of the relatively featureless terahertz region, where the higher frequency diffusional modes are strongly overlapped with librations and intermolecular vibrations. In the terahertz region, the signal-to-noise ratio of the OKE spectra is particularly high and the data show that there is a greater number of librational and intermolecular vibrational modes than previously detected. Of greatest interest though, is an intense low frequency (sub-alpha) relaxation that we show is in strong accordance with recent simulations that observe mesoscopic structure arising from aggregates or clusters; structure that explains the anomalous and inconveniently-high viscosities of these liquids.
Original languageEnglish
DOIs
Publication statusPublished - 2010
EventConference on Terahertz Technology and Applications III - San Francisco, United States
Duration: 27 Jan 201028 Jan 2010

Conference

ConferenceConference on Terahertz Technology and Applications III
CountryUnited States
CitySan Francisco
Period27/01/1028/01/10

Keywords

  • Terahertz spectroscopy
  • room-temperature ionic liquids
  • Kerr spectroscopy
  • dielectric relaxation spectroscopy

Cite this

Turton, D. A., Hunger, J., Stoppa, A., Hefter, G., Thoman, A., Walther, M., Buchner, R., Wynne, K., Sadwick, LP. (Ed.), & OSullivan, CMM. (Ed.) (2010). Terahertz dynamics of ionic liquids from a combined dielectric relaxation, terahertz, and optical Kerr effect study: evidence for mesoscopic aggregation. Paper presented at Conference on Terahertz Technology and Applications III, San Francisco, United States. https://doi.org/10.1117/12.840185