Ultrafast vibrational dynamics and energy transfer in imidazolium ionic liquids.

Femtosecond time-resolved coherent anti-Stokes Raman scattering (CARS) is used as a probe for monitoring the vibrational dynamics of room temperature ionic liquids (ILs). The experiments are performed on a series of 1,3-dialkylimidazolium ILs containing the bis(trifluoromethylsulfonyl)imide [NTf2] anion. The effect of methylation of the cationic C2 position on the dephasing time is studied analyzing [NTf2]-ILs of 1-ethyl-3-methylimidazolium [EMIM], 1-ethyl-2,3-dimethylimidazolium [EMMIM], 1-butyl-3-methylimidazolium [BMIM], and 1-butyl-2,3-dimethylimidazolium [BMMIM]. Raman coherences are excited around ∼1400 cm(-1), and the vibrational dephasing of the modes in the fingerprint region is monitored as a function of time. The results indicate that vibrational energy transfer occurs governed by the interionic interactions. This is suggested by mode beating involving vibrations beyond the excitation spectrum as well as systematic differences in the temporal dephasing behavior. In contrast, the length of the cationic alkyl side chain has a negligible impact on the vibrational dynamics.