We report on the achievement of wafer-level photocatalytic overall water splitting GaN nanowires grown by molecular beam epitaxy with incorporation Rh/Cr(2)O(3) core-shell nanostructures acting as cocatalysts, through which H(2) evolution is promoted noble metal core (Rh) while forming back reaction over Rh effectively prevented Cr(2)O(3) shell O(2) diffusion barrier. The decomposition pure into and confirmed to be a highly stable process, turnover number per unit time well exceeding value...

We have investigated the correlated surface electronic and optical properties of [0001]-oriented epitaxial InN nanowires grown directly on silicon. By dramatically improving growth process, we achieved, for first time, intrinsic both within bulk at nonpolar surfaces. The near-surface Fermi-level was measured to be ∼0.55 eV above valence band maximum undoped nanowires, suggesting absence electron accumulation pinning. This result is in direct contrast problematic degenerate two-dimensional...

A long-standing challenge in the design of single atom alloys (SAAs), for catalytic applications, is determination a feature space that maximally correlates to molecular binding energies per Sabatier principle. The more representative underlying properties, greater predictive capability given machine learning (ML) algorithm. Moreover, diversity and range SAA impurities/sites examined, difficulty arriving at such feature. In this work, we undertake examine degree which adsorbate electronic...

Electrocatalytic processes occurring at the heterogeneous interface are complex and their understanding molecular level remains challenging. Atomic force microscope (AFM) can detect interactions down to atomic level, but so far it has been mainly used obtain in-situ images of electrocatalysts. Here for first time, we employ AFM investigate gas evolution a platinum ultramicroelectrode (Pt UME) under electrochemical conditions using noise method. We excess when individual H2 bubble nucleation,...

In this work, we present a general theoretical and numerical approach for simultaneously solving the photovoltage photocurrent at semiconductor–liquid interfaces. Our methodology extends drift-diffusion methods developed metal–semiconductor Schottky contacts in device physics community into domain of "pseudo-Schottky" contacts. This model is applied to study photoelectrochemical anodes, utilized oxidative splitting water. To capture both interfaces, show that it necessary solve electron hole...

In this work, we present a theoretical study of surface state occupation statistics at semiconductor-liquid interfaces, as it pertains to the evolution H2 and O2 through water splitting. Our approach combines semiclassical charge transport electrostatics junction, with master rate equation describing mediated electron/hole transfer. As model system have studied TiO2-water junction in absence illumination, where is shown that states might not always equilibrate semiconductor. Non-trivial...

Recent studies have demonstrated the high efficiency through which nanostructured core–shell WO3/TiO2 (WT) heterojunctions can photocatalytically degrade model organic pollutants (stearic acid, QE ≈ 18% @ λ = 365 nm), and as such, has varied potential environmental antimicrobial applications. The key motivation herein is to connect theoretical calculations of charge transport phenomena, with experimental measures carrier behavior using transient absorption spectroscopy (TAS), develop a...

In this second paper, we develop transferable semiempirical extended Hückel theoretical (EHT) parameters for the electronic structure of another technologically important material, namely, silicon. The EHT are optimized to experimental target values band dispersion bulk We quantitatively benchmark our properties such as edge energies and locations, effective masses, spin-orbit coupling parameters, competitive with a nearest-neighbor sp3d5s* orthogonal tight-binding model silicon T. Boykin et...

The chemical dynamics of small polaron hopping within oxides is often interpreted through two-site variations on Marcus-Hush theory, while from a physics perspective more approached Holstein's solid-state formalism. Here we seek to provide chemically oriented viewpoint, focusing in oxides, concerning these two phenomenological frameworks by employing both tight-binding modelling and first-principles calculations. First, semiclassical approach the relations are overviewed as reduction model....

One of the main challenges in improving fast charging lithium-ion batteries is development suitable active materials for cathodes and anodes. Many suffer from unacceptable structural changes under high currents and/or low intrinsic conductivities. Experimental measurements are required to optimize these properties, but few techniques able spatially resolve ionic transport properties at small length scales. Here we demonstrate an atomic force microscope (AFM)-based technique measure local on...

To model polaronic behavior in strongly correlated transition-metal oxides with ab initio methods, one typically requires a level of theory beyond that local density or general gradient functional (DFT) approximations to account for the $d$-shell interactions oxides. In present work, we utilize additional on-site Hubbard corrections $(\mathrm{DFT}+U)$ calculate properties two lithium ion battery cathode materials, ${\mathrm{Li}}_{x}{\mathrm{FePO}}_{4}$ and...

We report on \textit{ab initio} electronic structure simulations of Li$_2$O$_2$, where 1.6% lithium atoms are substituted by silicon. It is demonstrated that this leads to the formation conducting impurity states in band gap Li$_2$O$_2$. show these originate from antibonding orbitals oxygen pairs and remarkably stable against possible polaron (upon electron injection). Through preemption mechanism, proposed compound expected significantly higher mobility than stoichiometric which could have...

In the present work, we study effects of electronic relaxation semicore levels on polaron activation energies and dynamics. Within framework adiabatic ab initio theory, utilize both static transition state theory molecular dynamics methods for an in-depth polaronic hopping in delithiated ${\text{LiFePO}}_{4} ({\text{FePO}}_{4})$. Our results show that states is significant ${\text{FePO}}_{4}$, resulting a lower barrier kinetics one to two orders faster compared result calculations do not...

In this work, we present an in situ method to probe the evolution of photoelectrochemically driven surface oxidation on photoanodes during active operation aqueous solutions. A standard solution K4Fe(CN)6-KPi was utilized benchmark photocurrent and assess progressive Ta3N5 various oxidizing manner, a proportional increase oxygen concentration detected with respect time further correlated continuous decline photocurrent. To discern how alters photocurrent, experimentally theoretically...

Herein we examine the low-bias electromigration wind force acting on quasi-one-dimensional nanoscale features within Landauer-B\"uttiker conduction picture. Ordinarily is calculated under approximation that nonequilibrium carrier distribution in vicinity of a defect same as bulk. However, this rooted assumption atomic scale defects scatter all incident electrons weakly (just and diffusely bulk). We by calculating mode-resolved transmission against Ag(111) step edges wires using...

Using ultrahigh vacuum (UHV) scanning tunneling microscopy (STM), many olefins have been shown to self-assemble on the hydrogen-passivated Si(100)-2 × 1 surface into one-dimensional nanostructures. This paper demonstrates that similar nanostructures can also be realized using alkynes. In particular, UHV STM, sum frequency generation (SFG), and density functional theory (DFT) are employed study growth mechanism binding configuration of phenylacetylene (PA) 1:H surface. Molecular-resolution...

In this work we present a theoretical connection between the Landauer picture utilized in quantum transport and Gerischer electrochemistry. A comprehensive analysis of single-particle total energy electrochemistry is presented, followed by derivation electron transfer rates utilizing nonequilibrium Green's function formalism. Correlations are also made with Marcus–Hush approach more often The limited to tunneling (also called outer-sphere) electrochemical reactions. general, it expected that...

We propose an atomistic model of electromigration (EM) in metals based on a recently developed phase-field-crystal (PFC) technique. By coupling the PFC model's atomic density field with applied electric through EM effective charge parameter, is successfully captured diffusive time scales. Our framework reproduces well-established phenomena known as Black's equation and Blech effect, also naturally captures commonly observed such void nucleation migration bulk crystals. A resistivity dipole...