Inferring ion cluster lifetimes from energy-resolved mass spectra of an EMI-BF4 electrospray plume

The fragmentation of ion clusters within the accelerating fields of ionic liquid ion sources (ILISs) is well documented and degrades ILIS performance and lifetime. Some of the most popular ILIS liquids, such as EMI-BF4 (1-Ethyl-3-methylimidazolium tetrafluoroborate) and EMI-Im (1-Ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide), emit clusters with lifetimes as low as similar to 1 ns. Studies of fragmentation within the accelerating field typically rely on measuring the plume energy distribution averaged over all plume species and comparing those measurements with numerical simulations to estimate ion cluster lifetimes. Here, for the first time, we estimate EMI-BF4 cluster lifetimes by analyzing the energy distributions of individual plume species. We use this novel analysis method to estimate mean lifetimes of positive EMI-BF4 ion clusters from previously published experimental data. We find that the mean lifetime ranges from tau = 3.7 ns to tau = 124 ns for [EMI+ ] [EMI-BF4 ] dimers and ranges from tau = 1.5 ns to tau = 23 ns for [ EM I+] [EMI - BF4](2) trimers. Fitting those data to an analytical fragmentation model, we estimate the binding energy and temperature as Delta G(S)(0) = 0.49 eV and T = 394 K for dimers and Delta G(S)(0) = 0.40 eV and T = 365 K for trimers. Comparing our results with previous studies supports the conclusion that clusters are emitted with a wide distribution of internal energies, contrary to the common assumption of single internal energy for each species. (c) 2024 Author(s).