Water/methanol solutions characterized by liquid μ-jet XPS and DFT—The methanol hydration case

The advent of liquid μ-jet setups as proposed by Faubel and Winter – in conjunction with X-ray Photoemission Spectroscopy (XPS) – has opened up a large variety of experimental possibilities in the field of atomic and molecular physics. In this study, we present first results from a synchrotron-based XPS core level and valence band electron spectroscopy study on water (10-4 M aqueous NaCl solution) as well as a water/methanol mixture using the newly commissioned ALBA liquid μ-jet setup. The experimental results are compared with simulations from density functional theory (DFT) regarding the electronic structure of single molecules, pure molecular clusters, and mixed clusters configurations as well as previous experimental studies. We give a detailed interpretation of the core level and valence band spectra for the vapour and liquid phases of both sample systems. The resulting overall picture gives insight into the water/methanol concentrations of the vapour and liquid phases as well as into the local electronic structure of the pertinent molecular clusters under consideration, with a special emphasis on methanol as the simplest amphiphilic molecule capable of creating hydrogen bonds. The electronic structure of water and methanol as vapours, liquids, as well as liquid mixture is determined using synchrotron-based X-ray photoemission spectroscopy on liquid μ-jets. These results together with density functional theory provide, among others, interesting insight into the hydration of these two molecules in the liquid phase mixture. [Display omitted] •The hydration of methanol has been characterized by liquid μ-jet XPS and DFT.•The amphiphilic character of methanol structures the surrounding water.•The methanol volume fraction for outer liquid layers exceeds the nominal bulk value.•The atomic/orbital contribution of the methanol/water mixture has been determined.•CH3OH•(H2O)3 cluster DFT model reproduces the observed binding energy shifts.