Mechanical properties of TiO2/carboxylic-acid interfaces from first-principles calculations.

Nature forms structurally complex materials with a large variation of mechanical and physical properties from only very few organic compounds and minerals. Nanocomposites made from TiO2 and carboxylic-acids, two substances that are available to nature as well as materials engineers, can be seen as representative of a huge class of natural and bio-inspired materials. The hybrid interfaces between the two components are thought to determine the overall properties of the composite. Yet, little is known about the atomistic processes at those interfaces under load and their failure mechanisms. The present work models the stress-strain curves of TiO2/carboxylic-acid interfaces in the slow deformation limit for different facets and binding modes, employing density functional theory calculations. Contrary to former hypotheses, the interface rarely fails through a de-bonding of the molecule, but rather through a surface failure mechanism. Furthermore, a stress-release mechanism is discovered for the bi-dentate binding mode on the {101} facet. Deriving mechanical properties, such as the interface strength, strain at interface failure, and the elastic modulus, allows a comparison with experimental results. The calculated strengths and elastic moduli already agree qualitatively with properties of nanocomposites, despite the simplifications in the model consisting of periodic sandwich structures. The results presented here will help to improve these materials and can be directly integrated in multi-scale simulations, in order to reach a more accurate quantitative description.

Oxidation-State Dynamics and Emerging Patterns in Magnetite.

Magnetite is an important mineral with many interesting applications related to its magnetic, electrical, and thermal properties. Typically studied by electronic structure calculations, these methods are unable to capture the complex ion dynamics at relevant temperatures, time, and length scales. We present a hybrid Monte Carlo/molecular dynamics (MC/MD) method based on iron oxidation-state swapping for accurate atomistic modeling of bulk magnetite, magnetite surfaces, and nanoparticles that captures the complex ionic dynamics. By comparing the oxidation-state patterns with those obtained from density functional theory, we confirmed the accuracy of our approach. Lattice distortions leading to the stabilization of excess charges and a critical surface thickness at which the oxidation states transition from ordered to disordered were observed. This simple yet efficient approach paves the way for elucidating aspects of oxidation-state ordering of inverse spinel structures in general and battery materials in particular.

Reconstructing the infrared spectrum of a peptide from representative conformers of the full canonical ensemble.

Leucine enkephalin (LeuEnk), a biologically active endogenous opioid pentapeptide, has been under intense investigation because it is small enough to allow efficient use of sophisticated computational methods and large enough to provide insights into low-lying minima of its conformational space. Here, we reproduce and interpret experimental infrared (IR) spectra of this model peptide in gas phase using a combination of replica-exchange molecular dynamics simulations, machine learning, and ab initio calculations. In particular, we evaluate the possibility of averaging representative structural contributions to obtain an accurate computed spectrum that accounts for the corresponding canonical ensemble of the real experimental situation. Representative conformers are identified by partitioning the conformational phase space into subensembles of similar conformers. The IR contribution of each representative conformer is calculated from ab initio and weighted according to the population of each cluster. Convergence of the averaged IR signal is rationalized by merging contributions in a hierarchical clustering and the comparison to IR multiple photon dissociation experiments. The improvements achieved by decomposing clusters containing similar conformations into even smaller subensembles is strong evidence that a thorough assessment of the conformational landscape and the associated hydrogen bonding is a prerequisite for deciphering important fingerprints in experimental spectroscopic data.

Surface structure of magnetite (111) under oxidizing and reducing conditions.

We report on differences in the magnetite (111) surface structure when prepared under oxidizing and reducing conditions. Both preparations were done under UHV conditions at elevated temperatures, but in one case the sample was cooled down while keeping it in an oxygen atmosphere. Scanning tunneling microscopy after each of the preparations showed a different apparent morphology, which is discussed to be an electronic effect and which is reflected in the necessity of using opposite bias tunneling voltages in order to obtain good images. Surface x-ray diffraction revealed that both preparations lead to Fe vacancies, leading to local O-terminations, the relative fraction of which depending on the preparation. The preparation under reducing conditions lead to a larger fraction of Fe-termination. The geometric structure of the two different terminations was found to be identical for both treatments, even though the surface and near-surface regions exhibit small compositional differences; after the oxidizing treatment they are iron deficient. Further evidence for the dependence of iron vs oxygen fractional surface terminations on preparation conditions comes from Fourier transform infrared reflection-absorption spectroscopy, which is used to study the adsorption of formic acid. These molecules dissociate and adsorb in chelating and bidentate bridging geometries on the Fe-terminated areas and the signal of typical infrared absorption bands is stronger after the preparation under reducing conditions, which results in a higher fraction of Fe-termination. The adsorption of formic acid induced an atomic roughening of the magnetite (111) surface which we conclude from the quantitative analysis of the crystal truncation rod data. The roughening process is initiated by atomic hydrogen, which results from the dissociation of formic acid after its adsorption on the surface. Atomic hydrogen adsorbs at surface oxygen and after recombination with another H this surface hydroxyl can form H2O, which may desorb from the surface, while iron ions diffuse into interstitial sites in the bulk.

Heterogeneous Adsorption and Local Ordering of Formate on a Magnetite Surface.

We report a novel heterogeneous adsorption mechanism of formic acid on the magnetite (111) surface. Our experimental results and density functional theory (DFT) calculations give evidence for dissociative adsorption of formic acid in quasibidentate and chelating geometries. The latter is induced by the presence of iron vacancies at the surface, making oxygen atoms accessible for hydrogen atoms from dissociated formic acid. DFT calculations predict that both adsorption geometries are energetically favorable under our experimental conditions. The calculations prove that the locally observed (√3 × âˆš3)R 30° superstructure consists of three formate molecules in a triangular arrangement, adsorbed predominantly in a chelating geometry. The results show how defects can stabilize alternative adsorption geometries, which is a crucial ingredient for a detailed atomistic understanding of reaction barriers on magnetite and other oxide surfaces, as well as for the stability of carboxylic acid based nanocomposite materials.

Direct and Broadband Plasmonic Charge Transfer to Enhance Water Oxidation on a Gold Electrode.

Plasmonic photocatalysis via hot charge carriers suffers from their short lifetime compared with the sluggish kinetics of most reactions. To increase lifetime, adsorbates on the surface of a plasmonic metal may create preferential states for electrons to be excited from. We demonstrate this effect with O adsorbates on a nanoporous gold electrode. Nanoporous gold is used to obtain a broadband optical response, to increase the obtained photocurrent, and to provide a SERS-active substrate. Only with adsorbates present, we observe significant photocurrents. Illumination also increases the adsorbate coverage above its dark potential-dependent equilibrium, as derived from a two-laser in situ SERS approach. Density functional theory calculations confirm the appearance of excitable states below the Fermi level. The photocurrent enhancement and broadband characteristics reveal the potential of the plasmonic approach to improve the efficiency of photoelectrochemical water splitting.

A first-principles analysis of the charge transfer in magnesium corrosion.

Magnesium is the lightest structural engineering material and bears high potential to manufacture automotive components, medical implants and energy storage systems. However, the practical use of untreated magnesium alloys is restricted as they are prone to corrosion. An essential prerequisite for the control or prevention of the degradation process is a deeper understanding of the underlying corrosion mechanisms. Prior investigations of the formation of gaseous hydrogen during the corrosion of magnesium indicated that the predominant mechanism for this process follows the Volmer-Heyrovský rather than the previously assumed Volmer-Tafel pathway. However, the energetic and electronic states of both reaction paths as well as the charge state of dissolved magnesium have not been fully unraveled yet. In this study, density functional theory calculations were employed to determine these parameters for the Volmer, Tafel and Heyrovský steps to gain a comprehensive understanding of the major corrosion mechanisms responsible for the degradation of magnesium.