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.

A recently developed force field for interactions of water molecules with the (110) surface of rutile (α-TiO2) has been generalized for atomistically detailed molecular dynamics simulations of the interfacial structure of the uncharged mineral surface in contact with liquid SPC/E water at 298 K and 1 atm and for negatively charged surfaces in contact with SPC/E water containing dissolved electrolyte ions (Rb+, Sr2+, Zn2+, Na+, Ca2+, Cl-). Both hydroxylated (dissociative) and nonhydroxylated (associative) surfaces are simulated, since both types of water−surface interactions have been postulated from ab initio calculations and spectroscopic studies under near-vacuum conditions. The positions of water molecules at the interface were found to be very similar for both hydroxylated and nonhydroxylated surfaces, with either terminal hydroxyl groups or associated water molecules occupying the site above each terminal titanium atom. Beyond these surface oxygens, a single additional layer of adsorbed water molecules occupies distinct sites related to the underlying crystal surface structure. The water structure and mobility quickly decay to the bulk liquid properties beyond this second layer. The hydrogen-bonding structure and water orientation in these first two oxygen layers are somewhat sensitive to the hydroxylation of the surface, as are the electrostatic profiles. For all simulated properties, including space-dependent diffusivity of water molecules, the influence of the interface is negligible beyond distances of about 15 Å from the surface. Increasing the temperature to 448 K while maintaining the density at the liquid−vapor saturated condition had minimal effect on the interfacial structure and electrostatic properties. These results are foundational to the simulation of dissolved ion interactions with the surface and the comparison of the simulation results with X-ray standing wave and crystal truncation rod measurements of water and electrolyte solutions in contact with rutile (110) single-crystal surfaces presented in Part 2 of this series.

A semitheoretical approach for the ionization constant of water, K W , is used to fit the available experimental data over wide ranges of density and temperature. Statistical thermodynamics is employed to formulate a number of contributions to the standard state chemical potential of the ionic hydration process. A sorption model is developed for calculating the inner-shell term, which accounts for the ion-water interactions in the immediate ion vicinity. A new analytical expression is derived using the Bragg-Williams approximation that reproduces the dependence of a mean ion solvation number on the solvent chemical potential. The proposed model was found to be correct at the zerodensity limit. The final formulation has a simple analytical form, includes seven adjustable parameters, and provides good fitting of the collected K W data, within experimental uncertainties, for a temperature range of 0-800°C and densities of 0-1.2 g cm Ϫ3 .

Periodic (CASTEP and DMol3) and cluster (Gaussian 98 and DMol3) ab initio calculations were carried out to develop force field parameters for the system Ti−O−H to model TiO2−H2O interfaces. A force field was derived from previously existing force fields for bulk TiO2 polymorphs (Matsui, M.; Akaogi, M. Mol. Simul. 1991, 6, 239) and water (SPC/E; Berendsen, H. J. C.; Grigera, J. R.; Straatsma, T. P. J. Phys. Chem. 1987, 91, 6269) that describes Ti in a variety of coordination environments, Ti−O−H bonding, and H-bonding on TiO2 surfaces. The force field was tested for its ability to reproduce ab initio structures of the hydrated (110) surface of α-TiO2 (rutile).

The detailed solvation structure at the (110) surface of rutile (alpha-TiO2) in contact with bulk liquid water has been obtained primarily from experimentally verified classical molecular dynamics (CMD) simulations of the ab initio-optimized surface in contact with SPC/E water. The results are used to explicitly quantify H-bonding interactions, which are then used within the refined MUSIC model framework to predict surface oxygen protonation constants. Quantum mechanical molecular dynamics (QMD) simulations in the presence of freely dissociable water molecules produced H-bond distributions around deprotonated surface oxygens very similar to those obtained by CMD with nondissociable SPC/E water, thereby confirming that the less computationally intensive CMD simulations provide accurate H-bond information. Utilizing this H-bond information within the refined MUSIC model, along with manually adjusted Ti-O surface bond lengths that are nonetheless within 0.05 A of those obtained from static density functional theory (DFT) calculations and measured in X-ray reflectivity experiments (as well as bulk crystal values), give surface protonation constants that result in a calculated zero net proton charge pH value (pHznpc) at 25 degrees C that agrees quantitatively with the experimentally determined value (5.4+/-0.2) for a specific rutile powder dominated by the (110) crystal face. Moreover, the predicted pHznpc values agree to within 0.1 pH unit with those measured at all temperatures between 10 and 250 degrees C. A slightly smaller manual adjustment of the DFT-derived Ti-O surface bond lengths was sufficient to bring the predicted pHznpcvalue of the rutile (110) surface at 25 degrees C into quantitative agreement with the experimental value (4.8+/-0.3) obtained from a polished and annealed rutile (110) single crystal surface in contact with dilute sodium nitrate solutions using second harmonic generation (SHG) intensity measurements as a function of ionic strength. Additionally, the H-bond interactions between protolyzable surface oxygen groups and water were found to be stronger than those between bulk water molecules at all temperatures investigated in our CMD simulations (25, 150 and 250 degrees C). Comparison with the protonation scheme previously determined for the (110) surface of isostructural cassiterite (alpha-SnO2) reveals that the greater extent of H-bonding on the latter surface, and in particular between water and the terminal hydroxyl group (Sn-OH) results in the predicted protonation constant for that group being lower than for the bridged oxygen (Sn-O-Sn), while the reverse is true for the rutile (110) surface. These results demonstrate the importance of H-bond structure in dictating surface protonation behavior, and that explicit use of this solvation structure within the refined MUSIC model framework results in predicted surface protonation constants that are also consistent with a variety of other experimental and computational data.

Periodic density functional theory (DFT) based on plane waves (PW) and Hartree−Fock (HF) based on the linear combination of atomic orbitals (LCAO) calculations using slabs separated by vacuum gaps were carried out to model the H2O−TiO2 (rutile) (110) interface. Positions of all atoms were allowed to relax except atoms in the central layer of the slab. Both associative and dissociative adsorption mechanisms were considered for half-monolayer and monolayer coverages. Five different orientations of H2O molecules on the TiO2 surface were studied to determine the most energetically favorable water positions for the associative mechanism. Two slab thicknesses (three Ti layers and five Ti layers) were chosen to test the effect of slab depth on calculated surface structures and adsorption energies. Results indicate that associative adsorption is favorable by −8 to −20 kJ/mol/H2O depending on the slab thickness for full-monolayer coverage. Embedded cluster HF calculations were also performed for comparison. Adsorption energies of H2O in the embedded cluster case are much more favorable for the associative mechanism. The role of H-bond formation on the adsorption energies and structures is discussed.

Plane wave density functional theory (DFT) calculations have been performed to study the atomic structure, preferred H2O adsorption sites, adsorption energies, and vibrational frequencies for water adsorption on the α-quartz (101) surface. Surface energies and atomic displacements on the vacuum-reconstructed, hydrolyzed, and solvated surfaces have been calculated and compared with available experimental and theoretical data. By considering different initial positions of H2O molecules, the most stable structures of water adsorption at different coverages have been determined. Calculated H2O adsorption energies are in the range −55 to −65 kJ/mol, consistent with experimental data. The lowest and the highest O−H stretching vibrational bands may be attributed to different states of silanol groups on the water-covered surface. The dissociation energy of the silanol group on the surface covered by the adsorption monolayer is estimated to be +80 kJ/mol. The metastable states for the protonated surface bridging O atoms (Obr), which may lead to hydrolysis of siloxane bonds, have been investigated. The calculated formation energy of a Q2 center from a Q3 center on the (101) surface with 2/3 dense monolayer coverage is equal to +70 kJ/mol which is in the range of experimental activation energies for quartz dissolution.

We study the relation between the hydrogen bonding and the vibrational frequency spectra of water on the (110) surface of rutile (R-TiO 2 ) with three structural layers of adsorbed water. Using ab initio molecular dynamics simulations at 280, 300, and 320 K, we find strong, crystallographically controlled adsorption sites, in general agreement with synchrotron X-ray and classical molecular dynamics simulations. We demonstrate that these sites are produced by strong hydrogen bonds formed between the surface oxygen atoms and the sorbed water molecules. The strength of these bonds is manifested by substantial broadening of the stretching mode vibrational band. The overall vibrational spectrum obtained from our simulations is in good agreement with inelastic neutron scattering experiments. We correlate the vibrational spectrum with different bonds at the surface to transform these vibrational measurements into a spectroscopy of surface interactions.