Energy Dissipation to Tungsten Surfaces upon Eley-Rideal Recombination of N2 and H2

Quasiclassical molecular dynamics simulations are performed to investigate energy dissipation to the (100) and (110) tungsten surfaces upon Eley-Rideal (ER) recombination of H2 and N2. Calculations are carried out within the single adsorbate limit under normal incidence. A generalized Langevin surface oscillator (GLO) scheme is used to simulate the coupling to phonons, whereas electron-hole (e-h) pair excitations are implemented using the local density friction approximation (LDFA). Phonon excitations are found to reduce the ER reactivity for N2 recombination, but do not affect H abstraction. In contrast, the effect of e-h pair excitations on the ER recombination cross section is small for N2, but can be important for H2. The analysis of the energy lost by the recombined species shows that most of the energy is dissipated into phonon excitations in the N2 recombination and into electronic excitations in the H2 recombination. In all cases, the energy dissipated into e-h pairs is taken away from the translational kinetic energy of the formed molecules, whereas dissipation to phonons, only significant for N2, also affects vibration. Interestingly, the electron mediated energy losses are found to be smaller in the case of N2 when surface motion is allowed

Random force in molecular dynamics with electronic friction

Originally conceived to describe thermal diffusion, the Langevin equation includes both a frictional drag and a random force, the latter representing thermal fluctuations first seen as Brownian motion. The random force is crucial for the diffusion problem as it explains why friction does not simply bring the system to a standstill. When using the Langevin equation to describe ballistic motion, the importance of the random force is less obvious and it is often omitted, for example, in theoretical treatments of hot ions and atoms interacting with metals. Here, friction results from electronic nonadiabaticity (electronic friction), and the random force arises from thermal electron–hole pairs. We show the consequences of omitting the random force in the dynamics of H-atom scattering from metals. We compare molecular dynamics simulations based on the Langevin equation to experimentally derived energy loss distributions. Despite the fact that the incidence energy is much larger than the thermal energy and the scattering time is only about 25 fs, the energy loss distribution fails to reproduce the experiment if the random force is neglected. Neglecting the random force is an even more severe approximation than freezing the positions of the metal atoms or modelling the lattice vibrations as a generalized Langevin oscillator. This behavior can be understood by considering analytic solutions to the Ornstein–Uhlenbeck process, where a ballistic particle experiencing friction decelerates under the influence of thermal fluctuations

Computerized Generation and Finite Element Stress Analysis of Endodontic Rotary Files

Introduction: The finite element method has been extensively used to analyze the mechanical behavior of endodontic rotary files under bending and torsional conditions. This methodology requires elevated computer-aided design skills to reproduce the geometry of the endodontic file, and also mathematical knowledge to perform the finite element analysis. In this study, an automated procedure is proposed for the computerized generation and finite element analysis of endodontic rotary files under bending and torsional conditions. Methods: An endodontic rotary file with a 25mm total length, 0.25mm at the tip, 1.20mm at 16mm from the tip, 2mm pitch and squared cross section was generated using the proposed procedure and submitted for analysis under bending and torsional conditions by clamping the last 3mm of the endodontic rotary file and applying a transverse load of 0.1N and a torsional moment of 0.3N.cm. Results: The results of the finite element analyses showed a maximum von Mises stress of 398MPa resulting from the bending analysis and a maximum von Mises stress of 843MPa resulting from the torsional analysis, both of which are next to the encastre point. Conclusions: The automated procedure allows an accurate description of the geometry of the endodontic file to be obtained based on its design parameters as well as a finite element model of the endodontic file from the previously generated geometry

Steric Hindrance of NH3 Diffusion on Pt(111) by Co-Adsorbed O-Atoms

A detailed velocity-resolved kinetics study of NH3 thermal desorption rates from p(2 × 2) O/Pt(111) is presented. We find a large reduction in the NH3 desorption rate due to adsorption of O-atoms on Pt(111). A physical model describing the interactions between adsorbed NH3 and O-atoms explains these observations. By fitting the model to the derived desorption rate constants, we find an NH3 stabilization on p(2 × 2) O/Pt(111) of 0.147–0.014+0.023 eV compared to Pt(111) and a rotational barrier of 0.084–0.022+0.049 eV, which is not present on Pt(111). The model also quantitatively predicts the steric hindrance of NH3 diffusion on Pt(111) due to co-adsorbed O-atoms. The derived diffusion barrier of NH3 on p(2 × 2) O/Pt(111) is 1.10–0.13+0.22 eV, which is 0.39–0.14+0.22 eV higher than that on pristine Pt(111). We find that Perdew Burke Ernzerhof (PBE) and revised Perdew Burke Ernzerhof (RPBE) exchange–correlation functionals are unable to reproduce the experimentally observed NH3–O adsorbate–adsorbate interactions and NH3 binding energies at Pt(111) and p(2 × 2) O/Pt(111), which indicates the importance of dispersion interactions for both systems

Morphosedimentary characterization of the Capbreton submarine canyon system, Bay of Biscay (Cantabrian Sea)

Various studies have been carried out to the declaration of new marine protected areas for their importance for habitats, according to the Natura 2000 Network. One of these sites is a sector of the Capbreton Submarine Canyon System, located in front of the Basque Country coast, in the Bay of Biscay (North Atlantic). During the Intemares_CapBreton 0619 and 0620 surveys; bathymetric, backscatter, high-resolution parametric data and samples of sediments, rocks and benthic communities from the seabed were acquired. The study was completed by recording video transects with the underwater vehicle ROTV Politolana from the IEO. The processing and analysis of the geophysical information has allowed obtaining a detailed bathymetry grid of 10 × 10 m, from which the first morphosedimentary characterization of the system of tributary canyons to the E-W trending main canyon and its interfluves has been made. One of the main features of this canyon system is the presence of a large pockmark field on adjacent platforms between canyons, located between 500 and 1000 m water depth. Within this field, pockmarks are shown as circular to elliptical depressions, most likely related to gas rich-fluid emissions to the subsurface.Versión del edito

First principles rates for surface chemistry employing exact transition state theory: application to recombinative desorption of hydrogen from Cu(111)

We present first principles calculations of the reactive flux for thermal recombinative desorption of hydrogen from Cu(111). We follow a theoretical paradigm used successfully for gas phase reactions, where electronic structure theory (DFT-GGA) is combined with transition state theory (TST). Classical ab initio molecular dynamics trajectories initiated from a thermal distribution near the transition state provide dynamical corrections to the desorption rate. We use this to calculate and study the recrossing error of TST and to directly simulate thermal desorption experiments based on a high temperature permeation method. Transition state recrossing is strongly temperature dependent and is even important in a frozen Cu-atom model. It is not influenced by inclusion of electron–hole pair excitation at the level of the local density electronic friction approximation. We also present the kinetic energy resolved flux of desorbing H2 at elevated temperature. This provides a more direct way to compare first principles theory to experiment, with no need to invoke detailed balance

Stereodynamics of Diatom Formation through Eley–Rideal Abstraction

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