Nonlinear vibrational spectroscopic studies on water/ionic liquid([Cnmim]TFSA: n = 4, 8) interfaces

Abstract

The interfaces of water/room temperature ionic liquids (RTIL) (1-alkyl-3-methyl imidazolium bis(trifluoromethylsulfonyl)amide ([C_nmim]TFSA): n = 4, 8) are investigated by infrared-visible sum frequency generation (IV-SFG) vibrational spectroscopy and molecular dynamics (MD) simulation. SFG spectra taken within the SO stretch region drastically differ between air/RTIL and water/RTIL interfaces. When a RTIL surface is in contact with water, a broadened and blue-shifted SO₂-ss mode peak is observed in the SFG spectra, indicating an inhomogeneous intermolecular interaction due to hydrogen bonding of the [TFSA]⁻ anions and water molecules at the water/[C_nmim]TFSA interface. MD simulations show the SO₂ groups of the anion are preferentially orientated toward the water phase, which is consistent with the SFG spectral features. Polar orientation of the [TFSA]⁻ anion originates from the ordered structure of the alkyl chains of [C_nmim]⁺ cations.