Abstract

The infrared (IR) spectra of ionic liquids involving 1-butyl-3-methylimidazolium (BMI) and the (CF₃SO₂)₂N⁻, BF₄⁻, or PF₆⁻ anions, recorded in the transmission and attenuated total reflection (ATR) modes, exhibit strong differences in the most intense anion absorption profiles. These distortions come from optical effects and make difficult any quantitative analysis of, for example, the antisymmetric stretching vibrations of the BF₄⁻ and PF₆⁻ anions. A method is proposed to determine the optical constants, from which any type of experimental spectrum can be simulated. It is then possible to use the anion vibrational bands as spectroscopic probes of the local interactions occurring in the neat ionic liquids and in solutions. This is illustrated by a direct identification of ion pairs and separated ions in the IR spectra of BMI–PF₆ solutions.

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