Ionic Liquid Vapors in Vacuum: Possibility to Derive Anodic Stabilities from DFT and UPS

[Image: see text] Ultraviolet photoelectron spectroscopy (UPS) investigations of several gas-phase ionic liquid (IL) ion pairs have been conducted. [EMIM][OTF], [PYR(14)][OTF], [EMIM][DCA], [PYR(14)][DCA], [PYR(14)][TCM], [PYR(14)][FSI], [PYR(14)][PF(6)], [S(222)][TFSI], [P(4441)][TFSI], and [EMMIM][TFSI] vapor UPS spectra are presented for the first time. The experimental low-binding-energy cutoff value (highest occupied molecular orbital, HOMO energy) of the ionic liquid ion pairs, which is of great interest, has been measured. Many studies use calculated gas-phase electronic properties to estimate the liquid-phase electrochemical stability. Hybrid density functional theory (DFT) calculations have been used to interpret the experimental data. The gas-phase photoelectron spectra in conjunction with the theoretical calculations are able to verify most HOMO energies and assign them to the cation or anion. The hybrid M06 functional is shown to offer a very good description of the ionic liquid electronic structure. In some cases, the excellent agreement between the UPS spectra and the M06 calculation validates the conformer found and constitutes as a first indirect experimental determination of ionic liquid ion-pair structure. Comparisons with recent theoretical studies are made, and implications for electrochemical applications are discussed. The new data provide a much-needed reference for future ab initio calculations and support the argument that modeling of IL cations and anions separately is incorrect.