Aqueous solutions of FeCl3 have been widely studied to shed light on a number of processes from dissolution, mineralization, biology, electrocatalysis, corrosion, to microbial biomineralization. Yet there are little to no molecular level studies of the air–liquid FeCl3 interface. Here, both aqueous and glycerol FeCl3 solution surfaces are investigated with polarized vibrational sum frequency generation (SFG) spectroscopy. We also present the first ever extreme ultraviolet reflection–absorption (XUV-RA) spectroscopy measurements of solvated ions and complexes at a solution interface, and observe with both X-ray photoelectron spectroscopy (XPS) and XUV-RA the existence of Fe­(III) at the surface and in the near surface regions of glycerol FeCl3 solutions, where glycerol is used as a high vacuum compatible proxy for water. XPS showed Cl– and Fe­(III) species with significant Fe­(III) interfacial enrichment. In aqueous solutions, an electrical double layer (EDL) of Cl– and Fe­(III) species at 0.5 m FeCl3 concentration is observed as evidenced from an enhancement of molecular ordering of water dipoles, consistent with the observed behavior at the glycerol surface. At higher concentrations in water, the EDL appears to be substantially repressed, indicative of further Fe­(III) complex enrichment and dominance of a centrosymmetric Fe­(III) species that is surface active. In addition, a significant vibrational red-shift of the dangling OH from the water molecules that straddle the air–water interface reveals that the second solvation shell of the surface active Fe­(III) complex permeates the topmost layer of the aqueous interface.

We report on the use of diffusion measurements to gauge the fluidity and surface binding properties of a molecular monolayer. The monolayer film consists of octadecyl-1-phosphonic acid (ODPA) and controlled amounts of a lyso-phosphatidic acid tagged with the fluorescent probe BODIPY (BLPA). The monolayer films were formed using a Langmuir-Blodgett (LB) trough and deposited onto a glass slide. Monolayer morphology was characterized during film formation using Brewster angle microscopy (BAM). Fluorescence Recovery After Photobleaching (FRAP) microscopy was used to measure translational diffusion of BLPA and Fluorescence Anisotropy Decay Imaging (FADI) was used to measure rotational diffusion of the BLPA chromophore. These results provide information on the motional freedom of the probe and, importantly, on the strength of interaction between the probe and the support. Compositional variations in the monolayer give rise to changes in constituent dynamics that reflect intermolecular interactions.

The translational diffusion dynamics of the zwitterionic lipid 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) at a planar phosphorylated support surface containing metal ions (Mg, Ca, Ba, Ni, Zn, Cd, Zr) was investigated using X-ray photoelectron spectroscopy (XPS) and fluorescence recovery after photobleaching (FRAP). Fluorescence recovery curves yielded diffusion constants on the order of 2-5 μm/s for the chromophore-tagged 12:0 NBD-Lyso-PC. Ionic interactions between the zwitterionic headgroup and metal ions were found to play a secondary role in mediating lipid fluidity. This work provides quantitative insight into the extent to which the fluidity of a supported lipid film is mediated by the ionic interactions between headgroup and surface versus that of the lipid-lipid tailgroup interactions.

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Ferric ion hydration differences are governed by ion pair formation uniquely affected by anion identity.