Abstract
The liquid–vacuum interfaces of a series of room-temperature ionic liquids (RTILs) containing the 1-alkyl-3-methylimidazolium cation ([Cnmim]) were investigated by reactive-atom scattering (RAS). The length of the alkyl chain (n = 4, 6, 8, and 12) and the anion type (bis(trifluoromethylsulfonyl)imide ([Tf2N]), trifluoromethanesulfonate ([OTf]), and tetrafluoroborate ([BF4])) were varied systematically to determine their effects on the preferential occupancy of the surface by alkyl chains. The experiments employed collisions with gas-phase, ground-state oxygen atoms, O(3P), generating OH and H2O products that revealed the abundance of abstractable H atoms at the liquid surface. Two complementary approaches with different O atom energies and detection methods were employed: we denote these RAS-laser-induced fluorescence (RAS-LIF) and RAS-mass spectrometry (RAS-MS). [Cnmim][BF4] RTILs were studied by both methods, giving consistent trends of strongly increasing alkyl coverage with chain length. Even for the ...
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