In Situ Liquid Secondary Ion Mass Spectrometry: A Surprisingly Soft Ionization Process for Investigation of Halide Ion Hydration

The understanding of ion solvation phenomena is of significance due to their influences on many important chemical, biological, and environmental processes. Mass spectrometry (MS)-based methods have been used to investigate this topic with molecular insights. As ion–solvent interactions are weak, ionization processes should be as soft as possible in order to retain solvation structures. An in situ liquid secondary ion MS (SIMS) approach developed in our group has been recently utilized in investigations of Li ion solvation in nonaqueous solution, and it detected a series of solvated Li ions. As traditionally SIMS has long been recognized as a hard ionization process with strong damage occurring at the sputtering interface, it is very interesting to study further how soft in situ liquid SIMS can be. In this work, we used halide ion hydration as an example to compare the ionization performance of the in situ liquid SIMS approach with regular electrospray ionization MS (ESI-MS). Results show that, although E...