No abstract

High-resolution specular x-ray reflectivity of the mica(001)-water interface under ambient conditions reveals oscillations in water oxygen density in the surface-normal direction, giving evidence of interfacial water ordering. The spacings between neighboring water layers in the near-surface, strongly oscillatory region are 2.5(2)-2.7(2) A, approximately the size of the water molecule. The density oscillations extend to about 10 A above the surface and do not strictly maintain a solvent-size periodicity as that in interfacial liquid metal and hard-sphere molecular liquids. We interpret this oscillatory density profile of the interfacial water as due to the "hard-wall" effect of the molecularly smooth mica surface.

Living organisms construct various forms of laminated nanocomposites through directed nucleation and growth of inorganics at self-assembled organic templates at temperatures below 100°C and in aqueous solutions. Recent research has focused on the use of functionalized organic surfaces to form continuous thin films of single-phase ceramics. Continuous thin films of mesostructured silicates have also been formed on hydrophobic and hydrophilic surfaces through a two-step mechanism. First, under acidic conditions, surfactant micellar structures are self-assembled at the solid/liquid interface, and second, inorganic precursors condense to form an inorganic-organic nanocomposite. Epitaxial coordination of adsorbed surfactant tubules is observed on mica and graphite substrates, whereas a random arrangement is observed on amorphous silica. The ability to process ceramic-organic nanocomposite films by these methods provides new technological opportunities.

A grazing incidence x-ray diffraction study of CH(3)(CH(2))(9)SH self-assembled on the (111) surface of gold revealed a disulfide head group structure, which provides a context in which to understand the structure and self-assembly process of this widely studied system. The structure consists of a nearly hexagonal two-dimensional arrangement of the hydrocarbon chains with a dimerization of the sulfur head groups (accommodated through a gauche bond), resulting in a S-S spacing of 2.2 angstroms. These results demonstrate the importance of internal molecular degrees of freedom in the templating of "soft" organic materials on inorganic substrates.

A comprehensive picture of the interface between aqueous solutions and the (110) surface of rutile (alpha-TiO2) is being developed by combining molecular-scale and macroscopic approaches, including experimental measurements, quantum calculations, molecular simulations, and Gouy-Chapman-Stern models. In situ X-ray reflectivity and X-ray standing-wave measurements are used to define the atomic arrangement of adsorbed ions, the coordination of interfacial water molecules, and substrate surface termination and structure. Ab initio calculations and molecular dynamics simulations, validated through direct comparison with the X-ray results, are used to predict ion distributions not measured experimentally. Potentiometric titration and ion adsorption results for rutile powders having predominant (110) surface expression provide macroscopic constraints of electrical double layer (EDL) properties (e.g., proton release) which are evaluated by comparison with a three-layer EDL model including surface oxygen proton affinities calculated using ab initio bond lengths and partial charges. These results allow a direct correlation of the three-dimensional, crystallographically controlled arrangements of various species (H2O, Na+, Rb+, Ca2+, Sr2+, Zn2+, Y3+, Nd3+) with macroscopic observables (H+ release, metal uptake, zeta potential) and thermodynamic/electrostatic constraints. All cations are found to be adsorbed as "inner sphere" species bonded directly to surface oxygen atoms, while the specific binding geometries and reaction stoichiometries are dependent on ionic radius. Ternary surface complexes of sorbed cations with electrolyte anions are not observed. Finally, surface oxygen proton affinities computed using the MUSIC model are improved by incorporation of ab initio bond lengths and hydrogen bonding information derived from MD simulations. This multitechnique and multiscale approach demonstrates the compatibility of bond-valence models of surface oxygen proton affinities and Stern-based models of the EDL structure, with the actual molecular interfacial distributions observed experimentally, revealing new insight into EDL properties including specific binding sites and hydration states of sorbed ions, interfacial solvent properties (structure, diffusivity, dielectric constant), surface protonation and hydrolysis, and the effect of solution ionic strength.

No abstract

No abstract

No abstract