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The electrical double layer (EDL) at aqueous solution-metal oxide interfaces critically affects many fundamental processes in electrochemistry, geology and biology, yet understanding its microscopic structure is challenging for both theory and experiments. Here we employ ab initio-based machine learning potentials including long-range electrostatics in large-scale atomistic simulations of the EDL at the TiO2-electrolyte interface. Our simulations provide a molecular-scale picture of the EDL that demonstrates the limitations of standard mean-field models. We further develop a method to accurately calculate the electrostatic potential drop at the interface. The computed capacitance originating from the adsorbed charges and the potential drop agrees with experiments, supporting the reliability of our description of the EDL. The larger interfacial capacitance of basic relative to acidic solutions originates from the higher affinity of the cations for the oxide surface and gives rise to distinct charging mechanisms on negative and positive surfaces.

The formation of ice in the atmosphere affects precipitation and cloud properties, and plays a key role in the climate of our planet. Although ice can form directly from liquid water at deeply supercooled conditions, the presence of foreign particles can aid ice formation at much warmer temperatures. Over the past decade, experiments have highlighted the remarkable efficiency of feldspar minerals as ice nuclei compared to other particles present in the atmosphere. However, the exact mechanism of ice formation on feldspar surfaces has yet to be fully understood. Here, we develop a first-principles machine-learning model for the potential energy surface aimed at studying ice nucleation at microcline feldspar surfaces. The model is able to reproduce with high fidelity the energies and forces derived from density-functional theory (DFT) based on the SCAN exchange and correlation functional. We apply the machine-learning force field to study different fully-hydroxylated terminations of the (100), (010), and (001) surfaces of microcline exposed to vacuum. Our calculations suggest that terminations that do not minimize the number of broken bonds are preferred in vacuum. We also study the structure of supercooled liquid water in contact with microcline surfaces, and find that water density correlations extend up to around 1 nm from the surfaces. Finally, we show that the force field maintains a high accuracy during the simulation of ice formation at microcline surfaces, even for large systems of around 30,000 atoms. Future work will be directed towards the calculation of nucleation free energy barriers and rates using the force field developed herein, and understanding the role of different microcline surfaces on ice nucleation., Comment: 12 pages, 6 figures

Two-dimensional (2D) metallic states induced by oxygen vacancies at oxide surfaces and interfaces provide new opportunities for the development of advanced applications, but the ability to control the behavior of these states is still limited. We used Angle Resolved Photoelectron Spectroscopy combined with density functional theory to study the reactivity of states induced by the oxygen vacancies at the (001)-(1x4) surface of anatase TiO2, where both 2D metallic and deeper lying in-gap states (IGs) are observed. Remarkably, the two states exhibit very different evolution when the surface is exposed to molecular O2: while IGs are almost completely quenched, the metallic states are only weakly affected. The energy scale analysis for the vacancy migration and recombination resulting from the DFT calculations confirms indeed that only the IGs originate from and remain localized at the surface, whereas the metallic states originate from subsurface vacancies, whose migration and recombination at the surface is energetically less favorable rendering them therefore insensitive to oxygen dosing.

Doping is one of the most common strategies for improving the photocatalytic and solar energy conversion properties of TiO$_2$, hence an accurate theoretical description of the electronic and optical properties of doped TiO$_2$ is of both scientific and practical interest. In this work we use many-body perturbation theory techniques to investigate two typical n-type dopants, Niobium and Hydrogen, in TiO$_2$ rutile. Using the GW approximation to determine band edges and defect energy levels, and the Bethe Salpeter equation for the calculation of the absorption spectra, we find that the defect energy levels form non-dispersive bands %associated with localized states lying $\simeq 2.2 eV$ above the top of the corresponding valence bands ($\simeq 0.9 eV$ below the conduction bands of the {\it pristine} material). The defect states are also responsible for the appearance of low energy absorption peaks that enhance the solar spectrum absorption of rutile. The spatial distributions of the excitonic wavefunctions associated with these low energy excitations are very different for the two dopants, suggesting a larger mobility of photoexcited electrons in Nb-TiO$_2$., Comment: 8 pages, 6 figures

Oxygen (O2) adsorbed on metal oxides is important in catalytic oxidation reactions, chemical sensing, and photocatalysis. Strong adsorption requires transfer of negative charge from oxygen vacancies (VOs) or dopants, for example. With scanning tunneling microscopy, we observed, transformed, and, in conjunction with theory, identified the nature of O2 molecules on the (101) surface of anatase (titanium oxide, TiO2) doped with niobium. VOs reside exclusively in the bulk, but we pull them to the surface with a strongly negatively charged scanning tunneling microscope tip. O2 adsorbed as superoxo (O2)- at fivefold-coordinated Ti sites was transformed to peroxo (O2)2- and, via reaction with a VO, placed into an anion surface lattice site as an (O2)O species. This so-called bridging dimer also formed when O2 directly reacted with VOs at or below the surface.

Anatase is a metastable polymorph of TiO$_2$. In contrast to the more widely-studied TiO$_2$ rutile, O vacancies (V$_\mathrm O$'s) are not stable at the anatase (101) surface. Low-temperature STM shows that surface V$_\mathrm O$'s, created by electron bombardment at 105 K, start migrating to subsurface sites at temperatures $\geq$ 200 K. After an initial decrease of the V$_\mathrm O$ density, a temperature-dependent dynamic equilibrium is established where V$_\mathrm O$'s move to subsurface sites and back again, as seen in time-lapse STM images. We estimate that activation energies for subsurface migration lie between 0.6 and 1.2 eV; in comparison, DFT calculations predict a barrier of ca. 0.75 eV. The wide scatter of the experimental values might be attributed to inhomogeneously-distributed subsurface defects in the reduced sample.

We use density functional theory (DFT) calculations to investigate structural models consisting of anatase TiO2(101) slabs covered by reduced overlayers formed by (101) crystallographic shear planes (CSPs). Ab initio thermodynamics supports the stability of these structures under a wide range of experimental conditions. The overlayers are found to have Ti2O3 stoichiometry with a crystal structure different from the known corundum-like Ti2O3 (here denoted {\alpha}-Ti2O3) phase. DFT calculations predict this new "csp-Ti2O3" phase to be energetically close to {\alpha}-Ti2O3 and to have also a similar band gap. These results suggest a possible role of the csp-Ti2O3 phase in the properties of black TiO2, a promising photocatalytic material made of nanoparticles with a crystalline TiO2 core and a highly reduced TiOx shell that is capable of absorbing the whole spectrum of visible light.

Water is of the utmost importance for life and technology. However, a genuinely predictive ab initio model of water has eluded scientists. We demonstrate that a fully ab initio approach, relying on the strongly constrained and appropriately normed (SCAN) density functional, provides such a description of water. SCAN accurately describes the balance among covalent bonds, hydrogen bonds, and van der Waals interactions that dictates the structure and dynamics of liquid water. Notably, SCAN captures the density difference between water and ice I{\it h} at ambient conditions, as well as many important structural, electronic, and dynamic properties of liquid water. These successful predictions of the versatile SCAN functional open the gates to study complex processes in aqueous phase chemistry and the interactions of water with other materials in an efficient, accurate, and predictive, ab initio manner.

We use first-principles calculations to investigate the adsorption and incorporation of non-metal impurities (N, C) at the anatase TiO$_2$(001)-(1$\times$4) reconstructed surface. We analyze in detail the influence of the surface structure and local strain on the impurity binding sites and incorporation pathways and identify important intermediates which facilitate impurity incorporation. We find various subsurface interstitial binding sites and corresponding surface $\rightarrow$ subsurface penetration pathways on the reconstructed surface. This surface also favors the presence of subsurface oxygen-vacancies, to which adsorbed species can migrate to form substitutional impurities. Most notably, we show that the non-exposed oxygen sites just below the surface have a key role in the incorporation of nitrogen and carbon in TiO$_2$(001)., Comment: 5 figures

Tricobalt tetraoxide (Co3O4) is an important catalyst and Co3O4(110) is a frequently exposed surface in Co3O4 nanomaterials. We employed Density-functional theory with on-site Coulomb repulsion U term to study the atomic structures, energetics, magnetic and electronic properties of the two possible terminations, A and B, of this surface. These calculations predict A as the stable termination in a wide range of oxygen chemical potentials, consistent with recent experimental observations. The Co3+ ions do not have a magnetic moment in the bulk, but become magnetic at the surface, which leads to surface magnetic orderings different from the one in the bulk. Surface electronic states are present in the lower half of the bulk band gap and cause partial metallization of both surface terminations. These states are responsible for the charge compensation mechanism stabilizing both polar terminations. The computed critical thickness for polarity compensation is 4 layers.

The spinel cobalt oxide Co3O4 is a magnetic semiconductor containing cobalt ions in Co2+ and Co3+ oxidation states. We have studied the electronic, magnetic and bonding properties of Co3O4 using density functional theory (DFT) at the Generalized Gradient Approximation (GGA), GGA+U, and PBE0 hybrid functional levels. The GGA correctly predicts Co3O4 to be a semiconductor, but severely underestimates the band gap. The GGA+U band gap (1.96 eV) agrees well with the available experimental value (~ 1.6 eV), whereas the band gap obtained using the PBE0 hybrid functional (3.42 eV) is strongly overestimated. All the employed exchange-correlation functionals predict 3 unpaired d electrons on the Co2+ ions, in agreement with crystal field theory, but the values of the magnetic moments given by GGA+U and PBE0 are in closer agreement with the experiment than the GGA value, indicating a better description of the cobalt localized d states. Bonding properties are studied by means of Maximally Localized Wannier Functions (MLWFs). We find d-type MLWFs on the cobalt ions, as well as Wannier functions with the character of sp3d bonds between cobalt and oxygen ions. Such hybridized bonding states indicate the presence of a small covalent component in the primarily ionic bonding mechanism of this compound., Comment: 24 pages, 8 figures

Recent theoretical work has provided evidence that hybrid functionals, which include a fraction of exact (Hartree Fock) exchange in the density functional theory (DFT) exchange and correlation terms, significantly improve the description of band gaps of semiconductors compared with local and semilocal approximations. Based on a recently developed order-$N$ method for calculating the exact exchange in extended insulating systems, we have implemented an efficient scheme to determine the hybrid functional band gap. We use this scheme to study the band gap and other electronic properties of the ternary compound In$_{1-x}$Ga$_{x}$N using a 64-atom supercell model., Comment: 3 figures, 2 tables

Exact (Hartree Fock) exchange is needed to overcome some of the limitations of local and semilocal approximations of density functional theory (DFT). So far, however, computational cost has limited the use of exact exchange in plane wave calculations for extended systems. We show that this difficulty can be overcome by performing a unitary transformation from Bloch to Maximally Localized Wannier functions in combination with an efficient technique to compute real space Coulomb integrals. The resulting scheme scales linearly with system size. We validate the scheme with representative applications., Comment: 6 pages, 3 figures, 3 tables

We present periodic Density Functional Theory calculations of the electronic properties of molecular junctions formed by amine-, and thiol-terminated alkane chains attached to two metal (Au, Ag) electrodes. Based on extensive analysis that includes molecular monolayers of varying densities, we establish a relationship between the alignment of the molecular energy levels and the interface dipoles, which shows that the band alignment (BA) in the limit of long, isolated chains is independent of the link group and can be computed from a reference system of non interacting molecule + metal electrodes. The main difference between the amine and thiol linkers is the effective dipole moment at the contact. This is very large, about 4.5 D, for amine linkers, leading to a strong dependence of the BA on the monolayer density and a slow convergence to the isolated molecule limit. Instead, this convergence is fast for S anchors due to the very small, ~ 0.2 D, effective dipoles at the contacts.

The formation of ordered phases of dimethyl-disulfide on the Au(111) surface has been investigated by means of Low-Energy Electron Diffraction (LEED), X-ray Photoemission Spectroscopy (XPS), and state-of-the-art Density Functional Theory (DFT) periodic supercell calculations. The LEED diffraction pattern, obtained after a production method that includes a two-step dosing and prolonged post-deposition annealing, unambiguously corresponds to a novel phase that consists of (3x4) domains coexisting with the as-deposited (sqrt3xsqrt3 )R30 structure. XPS measurements indicate that the coverage of the new (3x4) superstructure is the same as that of the (sqrt3xsqrt3)R30 phase. In both phases, the binding energy of the S 2p3/2 core-level peak is found to be 162.2 eV, corresponding to the formation of a thiolate layer. The DFT calculations allow us to identify a viable metastable (3x4) structure where the S headgroups of the CH3S radicals select distinct adsorption sites: three quarters of them adsorb at bridge sites and one quarter at top sites. The relative energetics of the (3x4) and (sqrt3xsqrt3)R30 configurations suggest that the two structures may coexist on the surface, in agreement with experimental data., Comment: 13 pages, 3 figures, pdf, submitted to J. Phys. Chem B as a Letter; removed reference and changed content

We present a density functional study of the structural and electronic properties of small Cu_n (n=1,4) aggregates on defect-free MgO(100). The calculations employ a slab geometry with periodic boundary conditions, supercells with up to 76 atoms, and include full relaxation of the surface layer and of all adsorbed atoms. The preferred adsorption site for a single Cu adatom is on top of an oxygen atom. The adsorption energy and Cu-O distance are E_S-A = 0.99 eV and d_S-A = 2.04 Angstroems using the Perdew-Wang gradient corrected exchange correlation functional. The saddle point for surface diffusion is at the "hollow" site, with a diffusion barrier of around 0.45 eV. For the adsorbed copper dimer, two geometries, one parallel and one perpendicular to the surface, are very close in energy. For the adsorbed Cu_3, a linear configuration is preferred to the triangular geometry. As for the tetramer, the most stable adsorbed geometry for Cu_4 is a rhombus. The adsorption energy per Cu atom decreases with increasing the size of the cluster, while the Cu-Cu cohesive energy increases, rapidly becoming more important than the adsorption energy., Comment: Major revision, Latex(2e) document, 23 pages, 11 figures, accepted for publication in J. of Chem. Phys., paper available at http://irrmawww.epfl.ch/vm/vm_work