Ultrafast vibrational spectroscopy (2D-IR) of CO{sub 2} in ionic liquids: Carbon capture from carbon dioxide’s point of view

The CO{sub 2}ν{sub 3} asymmetric stretching mode is established as a vibrational chromophore for ultrafast two-dimensional infrared (2D-IR) spectroscopic studies of local structure and dynamics in ionic liquids, which are of interest for carbon capture applications. CO{sub 2} is dissolved in a series of 1-butyl-3-methylimidazolium-based ionic liquids ([C{sub 4}C{sub 1}im][X], where [X]{sup −} is the anion from the series hexafluorophosphate (PF{sub 6}{sup −}), tetrafluoroborate (BF{sub 4}{sup −}), bis-(trifluoromethyl)sulfonylimide (Tf{sub 2}N{sup −}), triflate (TfO{sup −}), trifluoroacetate (TFA{sup −}), dicyanamide (DCA{sup −}), and thiocyanate (SCN{sup −})). In the ionic liquids studied, the ν{sub 3} center frequency is sensitive to the local solvation environment and reports on the timescales for local structural relaxation. Density functional theory calculations predict charge transfer from the anion to the CO{sub 2} and from CO{sub 2} to the cation. The charge transfer drives geometrical distortion of CO{sub 2}, which in turn changes the ν{sub 3} frequency. The observed structural relaxation timescales vary by up to an order of magnitude between ionic liquids. Shoulders in the 2D-IR spectra arise from anharmonic coupling of the ν{sub 2} and ν{sub 3} normal modes of CO{sub 2}. Thermal fluctuations in the ν{sub 2} population stochastically modulate the ν{sub 3} frequency and generate dynamic cross-peaks. These timescales are attributed to the breakup of ion cages that create a well-defined local environment for CO{sub 2}. The results suggest that the picosecond dynamics of CO{sub 2} are gated by local diffusion of anions and cations.