X-ray reflectivity from curved liquid interfaces.

X-ray reflectivity studies of the structure of liquid-vapour and liquid-liquid interfaces at modern sources, such as free-electron lasers, are currently impeded by the lack of dedicated liquid surface diffractometers. It is shown that this obstacle can be overcome by an alternative experimental approach that uses the natural curvature of a liquid drop for variation of the angle of incidence. Two modes of operation are shown: (i) sequential reflectivity measurements by a nanometre beam and (ii) parallel acquisition of large ranges of a reflectivity curve by micrometre beams. The feasibility of the two methods is demonstrated by studies of the Hg/vapour, H2O/vapour and Hg/0.1 M NaF interface. The obtained reflectivity curves match the data obtained by conventional techniques up to 5αc in micro-beam mode and up to 35αc in nano-beam mode, allowing observation of the Hg layering peak.

A novel X-ray diffractometer for studies of liquid-liquid interfaces.

The study of liquid-liquid interfaces with X-ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double-crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing-incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å(-1) in the surface normal and out to 14.8 Å(-1) in the in-plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X-ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.

In situ X-ray studies of adlayer-induced crystal nucleation at the liquid-liquid interface.

Crystal nucleation and growth at a liquid-liquid interface is studied on the atomic scale by in situ Å-resolution X-ray scattering methods for the case of liquid Hg and an electrochemical dilute electrolyte containing Pb(2+), F(-), and Br(-) ions. In the regime negative of the Pb amalgamation potential Φ(rp) = -0.70 V, no change is observed from the surface-layered structure of pure Hg. Upon potential-induced release of Pb(2+) from the Hg bulk at Φ > Φ(rp), the formation of an intriguing interface structure is observed, comprising a well-defined 7.6-Å-thick adlayer, decorated with structurally related 3D crystallites. Both are identified by their diffraction peaks as PbFBr, preferentially aligned with their axis along the interface normal. X-ray reflectivity shows the adlayer to consist of a stack of five ionic layers, forming a single-unit-cell-thick crystalline PbFBr precursor film, which acts as a template for the subsequent quasiepitaxial 3D crystal growth. This growth behavior is assigned to the combined action of electrostatic and short-range chemical interactions.