Vibrational Spectroscopy of Ionic Liquids

• Published in: Chemical reviews Vol. 117; no. 10; pp. 7053 - 7112
• Main Authors: Paschoal, Vitor H, Faria, Luiz F. O, Ribeiro, Mauro C. C
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 24-05-2017
• Subjects: Anions; Cations; Chemical compounds; Documents; Fluids; Infrared spectroscopy; Ionic interactions; Ionic liquids; Literature reviews; Molten salts; Phase transitions; Raman spectra; Recording; Salts; Spectroscopic analysis; Spectroscopy; Spectrum analysis; Temperature; Vibration; Vibrational spectra
• ISSN: 0009-2665; 1520-6890
• DOI: 10.1021/acs.chemrev.6b00461

Vibrational spectroscopy has continued use as a powerful tool to characterize ionic liquids since the literature on room temperature molten salts experienced the rapid increase in number of publications in the 1990’s. In the past years, infrared (IR) and Raman spectroscopies have provided insights on ionic interactions and the resulting liquid structure in ionic liquids. A large body of information is now available concerning vibrational spectra of ionic liquids made of many different combinations of anions and cations, but reviews on this literature are scarce. This review is an attempt at filling this gap. Some basic care needed while recording IR or Raman spectra of ionic liquids is explained. We have reviewed the conceptual basis of theoretical frameworks which have been used to interpret vibrational spectra of ionic liquids, helping the reader to distinguish the scope of application of different methods of calculation. Vibrational frequencies observed in IR and Raman spectra of ionic liquids based on different anions and cations are discussed and eventual disagreements between different sources are critically reviewed. The aim is that the reader can use this information while assigning vibrational spectra of an ionic liquid containing another particular combination of anions and cations. Different applications of IR and Raman spectroscopies are given for both pure ionic liquids and solutions. Further issues addressed in this review are the intermolecular vibrations that are more directly probed by the low-frequency range of IR and Raman spectra and the applications of vibrational spectroscopy in studying phase transitions of ionic liquids.