A density functional theory study of CO and atomic oxygen chemisorption on Pt(111)

Ab initio total energy calculations within a density functional theory framework have been performed for CO and atomic oxygen chemisorbed on the Pt(111) surface. Optimised geometries and chemisorption energies for CO and O on four high-symmetry sites, namely the top, bridge, fee hollow and hcp hollow sites, are presented, the coverage in all cases being 0.25 ML. The differences in CO adsorption energies between these sites are found to be small, suggesting that the potential energy surface for CO diffusion across Pt(111) is relatively flat. The 5 sigma and 2 pi molecular orbitals of CO are found to contribute to bonding with the metal. Some mixing of the 4 sigma and 1 pi molecular orbitals with metal states is also observed. For atomic oxygen, the most stable adsorption site is found to be the fee hollow site, followed in decreasing order of stability by the hcp hollow and bridge sites, with the top site being the least stable. The differences in chemisorption energies between sites for oxygen are larger than in the case of CO, suggesting a higher barrier to diffusion for atomic oxygen. The co-adsorption of CO and O has also been investigated. Calculated chemisorption energies for CO on an O/fcc-precovered surface show that of the available chemisorption sites, the top site at the oxygen atom's next-nearest neighbour surface metal atom is the most stable, with the other four sites calculated bring at least 0.29 eV less stable. The trend of CO site stability in the coadsorption system is explained in terms of a 'bonding competition' model. (C) 2000 Elsevier Science B.V. All rights reserved.

Recent fast electron energy transport experiments relevant to fast ignition inertial fusion

A number of experiments have been undertaken at the Rutherford Appleton Laboratory that were designed to investigate the physics of fast electron transport relevant to fast ignition inertial fusion. The laser, operating at a wavelength of 1054 nm, provided pulses of up to 350 J of energy on target in a duration that varied in the range 0.5-5 ps and a focused intensity of up to 10(21) W cm(-2). A dependence of the divergence of the fast electron beam with intensity on target has been identified for the first time. This dependence is reproduced in two-dimensional particle-in-cell simulations and has been found to be an intrinsic property of the laser-plasma interaction. A number of ideas to control the divergence of the fast electron beam are described. The fractional energy transfer to the fast electron beam has been obtained from calibrated, time-resolved, target rear-surface radiation temperature measurements. It is in the range 15-30%, increasing with incident laser energy on target. The fast electron temperature has been measured to be lower than the ponderomotive potential energy and is well described by Haines' relativistic absorption model.

On transition rates in surface hopping

Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a combined quantum electron-nuclear dynamics is still missing. In this work, we aim to elucidate the theoretical basis for the widely used hopping rules. Naturally, we concentrate thereby on the formal aspects of the TSH. Using a Gaussian wave packet limit, we derive the transition rates governing the hopping process at a simple avoided level crossing. In this derivation, which gives insight into the physics underlying the hopping process, some essential features of the standard TSH algorithm are retrieved, namely (i) non-zero electronic transition rate ("hopping probability") at avoided crossings; (ii) rescaling of the nuclear velocities to conserve total energy; (iii) electronic transition rates linear in the nonadiabatic coupling vectors. The well-known Landau-Zener model is then used for illustration. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4770280]

Characterization and parametrization in terms of atomic number of x-ray emission from K-shell filling during ion-surface interactions

When highly charged ions are incident on a surface, part of their potential energy is emitted as characteristic radiation. The energies and yields of these characteristic x rays have been measured for a series of elements at the Tokyo electron-beam ion trap. These data have been used to develop a simple model of the relaxation of the hollow atoms which are formed as the ion approaches the surface, as well as a set of semiempirical scaling laws, which allow for the ready calculation of the K-shell x-ray spectrum which would be produced by an arbitrary slow bare or hydrogenlike ion on a surface. These semiempirical scaling laws can be used to assess the merit of highly charged ion fluorescence x-ray generation in a wide range of applications.

Assessing the Potential for Saving Energy by Impersonating Idle Networked Devices

The idea of proxying network connectivity has been proposed as an efficient mechanism to maintain network presence on behalf of idle devices, so that they can “sleep”. The concept has been around for many years; alternative architectural solutions have been proposed to implement it, which lead to different considerations about capability, effectiveness and energy efficiency. However, there is neither a clear understanding of the potential for energy saving nor a detailed performance comparison among the different proxy architectures. In this paper, we estimate the potential energy saving achievable by different architectural solutions for proxying network connectivity. Our work considers the trade-off between the saving achievable by putting idle devices to sleep and the additional power consumption to run the proxy. Our analysis encompasses a broad range of alternatives, taking into consideration both implementations already available in the market and prototypes built for research purposes. We remark that the main value of our work is the estimation under realistic conditions, taking into consideration power measurements, usage profiles and proxying capabilities.

Strong parallel magnetic field effects on the hydrogen molecular ion

Equilibrium distances, binding energies and dissociation energies for the ground and low-lying states of the hydrogen molecular ion in a strong magnetic field parallel to the internuclear axis are calculated and refined, by using the two- dimensional pseudospectral method. High-precision results are presented for the binding energies over a wider field regime than already given in the literature (Kravchenko and Liberman 1997 Phys. Rev. A 55 2701). The present work removes a long- standing discrepancy for the R-eq value in the 1sigma(u) state at a field strength of 1.0 x 10(6) T. The dissociation energies of the antibonding 1pi(g) state induced by magnetic fields are determined accurately. We have also observed that the antibonding 1pi(g) potential energy curve develops a minimum if the field is sufficiently strong. Some unreliable results in the literature are pointed out and discussed. A way to efficiently treat vibrational processes and coupling between the nuclear and the electronic motions in magnetic fields is also suggested within a three-dimensional pseudospectral scheme.

Shedding Light on the light bulb puzzle: the role of attitudes and perceptions in the adoption of energy efficient light bulbs

Despite the potential energy savings and economic benefits associated with compact fluorescent light bulbs, their adoption by the residential sector has been limited to date. In this paper, we present a theoretical model that focuses on the agents' ability to perceive the correct cost of lighting and on the role of environmental attitudes as key determinants of the adoption decision. We use original data from Ireland to test our theoretical predictions. Our results emphasize the importance of education, information and environmental awareness in the adoption decision.

Large-scale density functional calculations of the surface properties of the Wigner crystal

The surface properties of the jellium model have been investigated by large supercell computations in the density functional theory-local spin-density (DFT-LSD) approach for planar slabs with up to 1000 electrons. A wide interval of densities has been explored, extending into the stability range of the Wigner crystal. Most computations have been carried out on nominally paramagnetic samples with an equal number of spin-up and spin-down electrons. The results show that within DFT-LSD spontaneous spin polarization and charge localization start nearly simultaneously at the surface for r(s) similar to 20, then, with decreasing density, they progress toward the center of the slab. Electrons are fully localized and spin polarized at r(s) = 30. At this density the charge distribution is the superposition of disjoint charge blobs, each corresponding to one electron. The distribution of blobs displays both regularities and disorder, the first being represented by well-defined planes and simple in-plane geometries, and the latter by a variety of surface defects. The surface energy, surface dipole, electric polarisability, and magnetization pattern have been determined as a function of density. All these quantities display characteristic anomalies at the density of the localization transition. The analysis of the low-frequency electric conductivity shows that in the fluid paramagnetic regime the in-plane current preferentially flows in the central region of the slab and the two spin channels are equally conducting. In the charge localized, spin-polarized regime, conductivity is primarily a surface effect, and an apparent asymmetry is observed in the two spin currents.

Using sketch-map coordinates to analyze and bias molecular dynamics simulations

When examining complex problems, such as the folding of proteins, coarse grained descriptions of the system drive our investigation and help us to rationalize the results. Oftentimes collective variables (CVs), derived through some chemical intuition about the process of interest, serve this purpose. Because finding these CVs is the most difficult part of any investigation, we recently developed a dimensionality reduction algorithm, sketch-map, that can be used to build a low-dimensional map of a phase space of high-dimensionality. In this paper we discuss how these machine-generated CVs can be used to accelerate the exploration of phase space and to reconstruct free-energy landscapes. To do so, we develop a formalism in which high-dimensional configurations are no longer represented by low-dimensional position vectors. Instead, for each configuration we calculate a probability distribution, which has a domain that encompasses the entirety of the low-dimensional space. To construct a biasing potential, we exploit an analogy with metadynamics and use the trajectory to adaptively construct a repulsive, history-dependent bias from the distributions that correspond to the previously visited configurations. This potential forces the system to explore more of phase space by making it desirable to adopt configurations whose distributions do not overlap with the bias. We apply this algorithm to a small model protein and succeed in reproducing the free-energy surface that we obtain from a parallel tempering calculation.

Simplifying the representation of complex free-energy landscapes using sketch-map

A new scheme, sketch-map, for obtaining a low-dimensional representation of the region of phase space explored during an enhanced dynamics simulation is proposed. We show evidence, from an examination of the distribution of pairwise distances between frames, that some features of the free-energy surface are inherently high-dimensional. This makes dimensionality reduction problematic because the data does not satisfy the assumptions made in conventional manifold learning algorithms We therefore propose that when dimensionality reduction is performed on trajectory data one should think of the resultant embedding as a quickly sketched set of directions rather than a road map. In other words, the embedding tells one about the connectivity between states but does not provide the vectors that correspond to the slow degrees of freedom. This realization informs the development of sketch-map, which endeavors to reproduce the proximity information from the high-dimensionality description in a space of lower dimensionality even when a faithful embedding is not possible.

In situ FTIRS investigations of surface processes of Rh electrode - Novel observation of geminal adsorbates of carbon monoxide on Rh electrode in acid solution

With the help of in situ multi-step FTIR Spectroscopy, two types of adsorbed geminal CO have been observed for the first time at an electrochemically modified Rh electrode. A doublet band of two broad peaks at 2166 and 2112cm is assigned to geminal CO on Rh surface oxide (or hydroxide) produced by the electrochemical modification process, and a doublet band of two peaks near 2103 and 2033cm is ascribed to geminal CO on surface clusters of Rh formed by reduction of Rh surface oxide. Based on the evolution of FTIR spectra with the electrode potential, the surface processes of a Rh electrode, subjected to a potential cycling treatment at 1.5Vs between -0.275 and 2.4V for 2min, have been elucidated. The present results at the solid/liquid electrochemical interface were compared with those obtained at the solid/gas interface, and consistent conclusions were achieved.

Cyclic nanoindentation and nano-impact fatigue characterisation of functionally graded TiN/TiNi shape memory film

This paper investigates the mechanism of nanoscale fatigue of functionally graded TiN/TiNi films using nano-impact and multiple-loading-cycle nanoindentation tests. The functionally graded films were deposited on silicon substrate, in which TiNi films maintain shape memory and pseudo elastic behavior, while a modified TiN surface layer provides tribological and anti-corrosion properties. Nanomechanical tests were performed to comprehend the localized film performance and failure modes of the functionally graded film using NanoTestTM equipped with Berkovich and conical indenter between 100 μN to 500 mN loads. The loading mechanism and load history are critical to define film failure modes (i.e. backward depth deviation) including the shape memory effect of the functionally graded layer. The results are sensitive to the applied load, loading type (e.g. semi-static, dynamic) and probe geometry. Based on indentation force-depth profiles, depth-time data and post-test surface observations of films, it is concluded that the shape of the nanoindenter is critical in inducing the localized indentation stress and film failure, including shape recovery at the lower load range. Elastic-plastic finite element (FE) simulation during nanoindentation loading indicated that the location of subsurface maximum stress near the interface influences the backward depth deviation type of film failure. A standalone, molecular dynamics simulation was performed with the help of a long range potential energy function to simulate the tensile test of TiN nanowire with two different aspect ratios to investigate the theory of its failure mechanism.

GRADIENT CORRECTIONS IN DENSITY-FUNCTIONAL THEORY CALCULATIONS FOR SURFACES - CO ON PD(110)

Ab initio total energy calculations have been performed for CO chemisorption on Pd(110). Local density approximation (LDA) calculations yield chemisorption energies which are significantly higher than experimental values but inclusion of the generalised gradient approximation (GGA) gives better agreement. In general, sites with higher coordination of the adsorbate to surface atoms lead to a larger degree of overbinding with LDA, and give larger corrections with GGA. The reason is discussed using a first-order perturbation approximation. It is concluded that this may be a general failure of LDA for chemisorption energy calculations. This conclusion may be extended to many surface calculations, such as potential energy surfaces for diffusion.

Molecular dynamics simulation (MDS) to study nanoscale machining processes

Molecular Dynamics Simulations (MDS) are constantly being used to make important contributions to our fundamental understanding of material behaviour, at the atomic scale, for a variety of thermodynamic processes. This chapter shows that molecular dynamics simulation is a robust numerical analysis tool in addressing a range of complex nanofinishing (machining) problems that are otherwise difficult or impossible to understand using other methods. For example the mechanism of nanometric cutting of silicon carbide is influenced by a number of variables such as machine tool performance, machining conditions, material properties, and cutting tool performance (material microstructure and physical geometry of the contact) and all these variables cannot be monitored online through experimental examination. However, these could suitably be studied using an advanced simulation based approach such as MDS. This chapter details how MD simulation can be used as a research and commercial tool to understand key issues of ultra precision manufacturing research problems and a specific case was addressed by studying diamond machining of silicon carbide. While this is appreciable, there are a lot of challenges and opportunities in this fertile area. For example, the world of MD simulations is dependent on present day computers and the accuracy and reliability of potential energy functions [109]. This presents a limitation: Real-world scale simulation models are yet to be developed. The simulated length and timescales are far shorter than the experimental ones which couples further with the fact that contact loading simulations are typically done in the speed range of a few hundreds of m/sec against the experimental speed of typically about 1 m/sec [17]. Consequently, MD simulations suffer from the spurious effects of high cutting speeds and the accuracy of the simulation results has yet to be fully explored. The development of user-friendly software could help facilitate molecular dynamics as an integral part of computer-aided design and manufacturing to tackle a range of machining problems from all perspectives, including materials science (phase of the material formed due to the sub-surface deformation layer), electronics and optics (properties of the finished machined surface due to the metallurgical transformation in comparison to the bulk material), and mechanical engineering (extent of residual stresses in the machined component) [110]. Overall, this chapter provided key information concerning diamond machining of SiC which is classed as hard, brittle material. From the analysis presented in the earlier sections, MD simulation has helped in understanding the effects of crystal anisotropy in nanometric cutting of 3C-SiC by revealing the atomic-level deformation mechanisms for different crystal orientations and cutting directions. In addition to this, the MD simulation revealed that the material removal mechanism on the (111) surface of 3C-SiC (akin to diamond) is dominated by cleavage. These understandings led to the development of a new approach named the “surface defect machining” method which has the potential to be more effective to implement than ductile mode micro laser assisted machining or conventional nanometric cutting.