Early Microjet Experimentation with Liquid Water in Vacuum.

Abstract

ConspectusIn this brief look at the history of liquid microjets, I recollect some personal reminiscences on initial challenges for introduction of this method, as well as unexpected problems and exemplary results using this new tool for liquid evaporation and photoelectron spectroscopy studies.Many efficient and direct, atomic level diagnostic instruments in use at solid state surfaces and in gas-phase atom or cluster studies require high vacuum. They have therefore not been applied to investigations of aqueous solutions because liquid water both strongly evaporates and rapidly freezes in vacuum. Only fairly recently, over the past three decades, have liquid microjets been considered as practicable targets for research on liquid-water interfaces in vacuum. The working principle is analogous to the functioning of a free molecular beam source, where molecules enter through a small aperture into a vacuum without being disturbed by subsequent collisions in their original Maxwellian velocity distribution. Similarly, above a microjet surface in vacuum, water vapor molecules do not interact with each other, or with different probe particles, as long as the liquid jet diameter is small in relation to the mean free path of the liquids' vapor at equilibrium conditions. For pure liquid water, this constraint is Djet < λvap < 10 μm for 6.1 mbar vapor pressure at the triple point of water. A high streaming velocity of the liquid jet, >50 m/s, delays freezing and exposes a steadily renewed fresh vacuum surface for experiments.For experimental verification of the microjet free surface concept, H2O vapor velocities were measured in a molecular beam time-of-flight experiment. These studies showed Maxwellian velocity distributions with the expected local water-jet temperatures for 5 and 10 μm jets, whereas larger liquid jet diameters of 50 μm exhibit narrowed vapor velocity profiles. This narrowing is the known signature of incipient, collision dominated, supersonic hydrodynamic expansions in nozzle beam sources. As a completely unexpected new result in evaporation studies of carboxylic acid solutions, freely evaporating acetic acid dimers showed apparent non-equilibrium liquid surface source temperatures several hundred kelvin above the simultaneously measured monomer temperatures, a phenomenon shown to be correlated with surface tension.Continuing with improvements, the vacuum water microjets were implemented inside a photoelectron spectroscopy apparatus that was modified for handling large amounts of water vapor. After initial complications with liquid jet charging phenomena, the first partial liquid-water photoelectron spectra were recorded using 21 eV photons from a He I discharge lamp. In the next step, the equipment was taken to a synchrotron radiation beamline at BESSY II, resulting in substantial improvements of signal intensity and in photon tunability for narrow band monochromatic soft X-rays up to 1 keV. Two early examples of these continuing experiments are considered, briefly, for aqueous alkali halide salt solutions and for the pH-value dependent protonation of an NH2/NH3+ group in an amino acid directly in a photoelectron spectrum of a solution.In conclusion, liquid microjets have opened up a completely new approach to studies of arbitrary liquids with chemical and biological relevance.