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The dissociation of methane is not only an important reaction step in catalytic processes, but also of fundamental interest. Dynamical effects during the dissociative chemisorption of methane on metal surfaces cause significant differences in computed reaction rates, compared to what is predicted by typical transition state theory (TST) models. It is clear that for a good understanding of the catalytic activation of methane dynamical simulations are required. In this paper, a general blueprint is provided for performing dynamical simulations of the dissociative chemisorption of methane on metal surfaces, by employing either the quasi-classical trajectory or ring polymer molecular dynamics approach. If the computational setup is constructed with great care-since results can be affected considerably by the setup - chemically accurate predictions are achievable. Although this paper concerns methane dissociation, the provided blueprint is, so far, applicable to the dissociative chemisorption of most molecules. [ABSTRACT FROM AUTHOR]

The laser surface texturing (LST) technique has recently been used to enhance adhesion bond strength in various coating applications and to create structures with controlled hydrophobic or superhydrophobic surfaces. The texturing processing parameters can be adjusted to tune the surface's polarity, thereby controlling the ratio between the polar and dispersed components of the surface free energy and determining its hydrophobic character. The aim of this work is to systematically select appropriate laser and scan head parameters for high-quality surface topography of metal-based materials. A correlation between texturing parameters and wetting properties was made in view of several technological applications, i.e., for the proper growth of conformal layers onto laser-textured metal surfaces. Surface analyses, carried out by scanning electron microscopy and profilometry, reveal the presence of periodic microchannels decorated with laser-induced periodic surface structures (LIPSS) in the direction parallel to the microchannels. The water contact angle varies widely from about 20° to 100°, depending on the treated material (titanium, nickel, etc.). Nowadays, reducing the wettability transition time from hydrophilicity to hydrophobicity, while also changing environmental conditions, remains a challenge. Therefore, the characteristics of environmental dust and its influence on the properties of the picosecond laser-textured surface (e.g., chemical bonding of samples) have been studied while monitoring ambient conditions. [ABSTRACT FROM AUTHOR]

This study focuses on depositing Ni/W-Al2O3 nanocomposites onto a low-carbon substrate using the pulse electrodeposition technique. The effects of pulse current density on microstructural characteristics, microhardness, phase structure, and wear/corrosion properties of Ni/W-Al2O3 nanocomposites were investigated. Among the investigated nanocomposites, Ni/W-Al2O3 deposited at 0.6 A/dm2 current density showed the finest structure with average Ni-W grain and Al2O3 nanoparticle sizes of 66.7 nm and 39.1 nm, respectively. The Ni/W-Al2O3 nanocomposite deposited under the same conditions exhibited a maximum microhardness of ~ 825.7 HV, while also demonstrating the lowest corrosion current density of ~ 0.72 A/cm2. After 60 min of wear testing, wear loss of Ni/W-Al2O3 nanocomposite deposited at 0.6 A/dm2 was recorded as 42.8 mg, indicating its excellent wear resistance. In contrast, Ni/W-Al2O3 nanocomposite deposited at 0.8 A/dm2 displayed the highest wear loss value of 101.5 mg. [ABSTRACT FROM AUTHOR]

We studied the surface-enhanced Raman spectra of amino acids D-alanine and DL-serine and their mixture on silver nanoisland films (SNF) immersed in phosphate-buffered saline (PBS) solution at millimolar amino acid concentrations. It is shown that the spectra from the amino acid solutions differ from the reference spectra for microcrystallites due to the electrostatic orientation of amino acid zwitterions by the metal nanoisland film. Moreover, non-additive peaks are observed in the spectrum of the mixture of amino acids adsorbed on SNF, which means that intermolecular interactions between adsorbed amino acids are very significant. The results indicate the need for a thorough analysis of the Raman spectra from amino acid solutions, particularly, in PBS, in the presence of a nanostructured silver surface, and may also be of interest for studying molecular properties and intermolecular interactions. [ABSTRACT FROM AUTHOR]

In this study, we demonstrate the structural evolution of a two-dimensional (2D) supramolecular assembly system, which is steered by the thermally activated deprotonation of the primary organic building blocks on a Ag(111) surface. Scanning tunneling microscopy revealed that a variety of structures, featuring distinct structural, chiral, and intermolecular bonding characters, emerged with the gradual thermal treatments. According to our structural analysis, in combination with density function theory calculations, the structural evolution can be attributed to the successive deprotonation of the organic building blocks due to the inductive effect. Our finding offers a facile strategy towards controlling the supramolecular assembly pathways and provides a comprehensive understanding of the 2D crystal engineering on surfaces. [ABSTRACT FROM AUTHOR]

Electrocatalytic denitrification is a promising technology for removing NOx species (NO3−, NO2− and NO). For NOx electroreduction (NOxRR), there is a desire for understanding the catalytic parameters that control the product distribution. Here, we elucidate selectivity and activity of catalyst for NOxRR. At low potential we classify metals by the binding of *NO versus *H. Analogous to classifying CO2 reduction by *CO vs. *H, Cu is able to bind *NO while not binding *H giving rise to a selective NH3 formation. Besides being selective, Cu is active for the reaction found by an activity‐volcano. For metals that does not bind NO the reaction stops at NO, similar to CO2‐to‐CO. At potential above 0.3 V vs. RHE, we speculate a low barrier for N coupling with NO causing N2O formation. The work provides a clear strategy for selectivity and aims to inspire future research on NOxRR. [ABSTRACT FROM AUTHOR]

Electrocatalytic denitrification is a promising technology for removing NOx species (NO3−, NO2− and NO). For NOx electroreduction (NOxRR), there is a desire for understanding the catalytic parameters that control the product distribution. Here, we elucidate selectivity and activity of catalyst for NOxRR. At low potential we classify metals by the binding of *NO versus *H. Analogous to classifying CO2 reduction by *CO vs. *H, Cu is able to bind *NO while not binding *H giving rise to a selective NH3 formation. Besides being selective, Cu is active for the reaction found by an activity‐volcano. For metals that does not bind NO the reaction stops at NO, similar to CO2‐to‐CO. At potential above 0.3 V vs. RHE, we speculate a low barrier for N coupling with NO causing N2O formation. The work provides a clear strategy for selectivity and aims to inspire future research on NOxRR. [ABSTRACT FROM AUTHOR]

[Display omitted] • For both surfaces, the neutral fractions decrease as the incident energy increases. • Neutral fraction on H 2 O/Cu(1 1 0) is lower than that of Cu(1 1 0). • The work function of H 2 O/Cu(1 1 0) is lightly greater than that of clean Cu(1 1 0). keV-energy Na+ ions are scattered from clean and water covered Cu(1 1 0) surfaces in grazing incidence. For both surfaces the pronounced Na° fractions decrease with incident energy. In particular, the lower Na° fraction has been observed for the water covered Cu(1 1 0) surface. The simple calculations using rate equation are presented to compare with the experimental data. The calculation is in agreement with the experimental data. It indicates that the water covered Cu(1 1 0) surface has the slightly higher work function due to water molecules dissociation and forming hydroxyl groups, so that the neutral fraction on water covered Cu(1 1 0) is lower than that on the clean surface. [ABSTRACT FROM AUTHOR]

Purpose: We investigated the recovery and extraction efficiency of DNA from three metal surfaces (brass, copper, steel) relevant to forensic casework, and plastic (control) using two different swabbing systems; Rayon and Isohelix™ swabs, with sterile water and isopropyl alcohol respectively, as the wetting solutions. Methods: Twenty nanograms of human genomic DNA were applied directly to Isohelix™ and Rayon swabs; and to the metal and plastic substrates. All substrates were left to dry for 24 h, followed by single wet swabbing and extraction with the DNA IQ™ System. DNA extracts were quantified using real time quantitative PCR assays with SYBR green chemistry. Results: DNA was extracted from directly seeded Isohelix™ swabs with a high efficiency of 98%, indicating effective DNA-release from the swab into the extraction buffer. In contrast, only 58% of input DNA was recovered from seeded Rayon swabs, indicating higher DNA retention by these swabs. Isohelix™ swabs recovered 32 – 53% of DNA from metal surfaces, whilst the Rayon swabs recovered 11—29%. DNA recovery was lowest from copper and highest from brass. Interestingly, Rayon swabs appeared to collect more DNA from the plastic surface than Isohelix™ swabs, however, due to the lower release of DNA from Rayon swabs they returned less DNA overall following extraction than Isohelix™ swabs. Conclusion: These results demonstrate that DNA samples deposited on metal surfaces can be more efficiently recovered using Isohelix™ swabs wetted with isopropyl alcohol than Rayon swabs wetted with sterile water, although recovery is affected by the substrate type. [ABSTRACT FROM AUTHOR]

Jellium model is well known and used to understand the neutralization of alkali-metal ions on metal surfacesbut we find it cannot explain our experiments for the neutralization of 0.4 keV and 0.8 keV Na+ ions on Al(1 1 1) and Cu(1 1 0) surfaces in grazing incidence. As the exit angle increases neutral fractions on Cu(1 1 0) surface decreases first and then increases which is similar to our previous results at large scattering angles. While for the Al(1 1 1) surface we observe opposite characteristics. This anomalous bell-shaped feature cannot be explained by the Jellium model. One possible explanation is the inner 2p electron promotion at smaller exit angles this may cause the Na* excited states to be generated and produce excess Na+ ions while the similar electronic excitation process is inefficient for the Cu(1 1 0) surface in the present energy range. [ABSTRACT FROM AUTHOR]

The characteristics of different shapes of nonmetallic inclusions (NMIs) are determined using different methods. In this respect, various shapes of NMIs, including spherical, octahedral, elongated, bar‐like, plate‐like, polyhedral, and irregular inclusions, are observed in different steels and ferroalloys. The inclusions are investigated using three methods: 1) 2D investigations on a polished cross section (2D method); 2) 3D investigations on a film filter after electrolytic extraction and filtration (EE method); and 3) 3D investigations on a metal surface after electrolytic extraction (MS method). In addition, scanning electron microscopy (SEM) with an energy‐dispersive spectrometer (EDS) is used for the determination of the chemical composition of inclusions. The advantages and limitations of different methods for investigations of different shaped inclusions are discussed. The results show that the 2D method is less precise to detect the morphology, size, and number of inclusions; however, the EE and MS methods are used to determine a more accurate morphology. Furthermore, the MS method is found to be more advantageous in detecting large‐sized inclusions. This study also shows that the results on both the film filter and metal surface should be grouped together to obtain more comprehensive information of the inclusion characteristics. [ABSTRACT FROM AUTHOR]

The modification of metal electrode surfaces with functional organic molecules is an important part of organic electronics. The interaction of the buckminsterfullerene fragment molecule pentaindenocorannulene with a Cu(100) surface is studied by scanning tunneling microscopy, dispersion‐enabled density functional theory, and force field calculations. Experimental and theoretical methods suggest that two adjacent indeno groups become oriented parallel to the surface upon adsorption under mild distortion of the molecular frame. The binding mechanism between molecule and surface is dominated by strong electrostatic interaction owing to Pauli repulsion. Two‐dimensional aggregation at room temperature leads to a single lattice structure in which all molecules are oriented unidirectionally. Their relative arrangement in the lattice suggests noncovalent intermolecular interaction through C−H⋅⋅⋅π bonding. [ABSTRACT FROM AUTHOR]

The salinization and contamination of metal surfaces by chloride‐containing aerosols is of great importance with regard to corrosion phenomena of damaged coated metal surfaces and stainless steels in the maritime sector and in offshore applications. Detailed questions have to be answered to clarify whether and to what extent salinization of the surface has an influence on the adhesion and durability of coatings in repairing applications and on pitting occurrence on stainless steels under atmospheric conditions. The questions arise which degree of salinization is reached after which period of time and how a defined and reproducible salinization can be simulated in the laboratory for further systematic investigations. The article is dedicated to these questions. Results of a field trial on the Island of Heligoland are presented and a simple procedure for a defined loading of metal surfaces with chlorides at a laboratory scale using a design of experiments (DoE) approach is introduced. [ABSTRACT FROM AUTHOR]

[Display omitted] • Deposition rate affects roughness, activation barrier influences. • Unrestricted diffusion model leads to higher roughness. • Temperature smooth surfaces, alters growth mechanisms. • Higher temperatures increase layer occupancy, favor diffusion. • Steady state is not reached for any materials in unrestricted model. • Dynamic exponent Beta depends of the diffusion mechanism. The growth behavior of Cr and W surfaces using kinetic Monte Carlo (KMC) simulations based on Density-Functional Theory (DFT) is presented in this study. Three models, a growth model with random deposition and no diffusion, a growth model with restricted diffusion and a growth model with unrestricted diffusion model, were compared to understand their influence on the predicted surface roughness and layer density. The impact of deposition rate and temperature on surface growth for both metals were analyzed. For deposition rate studies, five different rates (0.01 ML/s, 0.1 ML/s, 1.0 ML/s, 10.0 ML/s, and 100 ML/s) were considered at 550 K for Cr and W respectively. The effect of temperature on roughness was also studied employing various temperatures from 300 K to 1100 K for both metals and under the two different evolution models. The results show that the unrestricted diffusion model exhibits higher roughness compared to the restricted model for both metals. The restricted model shows a stable region of roughness, whereas the unrestricted model shows a continuous increase in roughness throughout the simulation. Furthermore, layer density analysis revealed that temperature affects the filling of lower monolayers. Finally, dynamic exponents β and α for each studied model were calculated and discussed. The results highlight the influence of diffusion models, deposition rate and temperature on surface, roughness, and layer density. [ABSTRACT FROM AUTHOR]

Inert metal surfaces present more chances of hosting organic intact radicals than other substrates, but large amounts of delocalized electronic states favor charge transfer and thus spin quenching. Lowering the molecule–substrate interaction is a usual strategy to stabilize radicals on surfaces. In some works, thin insulating layers were introduced to provide a controllable degree of electronic decoupling. Recently, retinoid molecules adsorbed on gold have been manipulated with a scanning tunneling microscope (STM) to exhibit a localized spin, but calculations failed to find a radical derivative of the molecule on the surface. Now the formation of a neutral radical spatially localized in a tilted and lifted cyclic end of the molecule is presented. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated allene in its lifted subpart. DFT calculations and STM manipulations give support to the proposed mechanism. Spinning on the surface: An allene formed by a sigmatropic reaction on retinoic acid shows a long‐lived magnetism on a gold surface after dehydrogenation. An allene moiety provokes a perpendicular tilt of the cyclic end relative to the rest of the conjugated chain, thus localizing the spin of the dehydrogenated product in its lifted subpart. [ABSTRACT FROM AUTHOR]

Abstract We review our recent studies of photochemistry and plasmon chemistry of dimethyl disulfide, (CH 3 S) 2 , molecules adsorbed on metal surfaces using a scanning tunneling microscope (STM). The STM has been used not only for the observation of surface structures at atomic spatial resolution but also for local spectroscopies. The STM combined with optical excitation by light can be employed to investigate chemical reactions of single molecules induced by photons and localized surface plasmons. This technique allows us to gain insights into reaction mechanisms at a single molecule level. The experimental procedures to examine the chemical reactions using the STM are briefly described. The mechanism for the photodissociation reaction of (CH 3 S) 2 molecules adsorbed on metal surfaces is discussed based on both the experimental results obtained with the STM and the electronic structures calculated by density functional theory. The dissociation reaction of the (CH 3 S) 2 molecule induced by the optically excited plasmon in the STM junction between a Ag tip and metal substrate is also described. The reaction mechanism and pathway of this plasmon-induced chemical reaction are discussed by comparison with those proposed in plasmon chemistry. [ABSTRACT FROM AUTHOR]

Understanding the behavior of proteins at material interfaces has become increasingly important as the intersection between the biological and synthetic worlds continues to grow. By inducing changes in protein structure, interactions with materials may lead to a loss of function and/or biological activity, as well as undesirable cellular interactions in vivo , including the foreign body reaction to implantable materials. Despite extensive research, the understanding of the mechanisms that lead to protein conformational changes on surfaces remains incomplete. Here, we highlight recent advances in understanding and controlling protein conformation on the surface of synthetic materials, including nanomaterials, polymer films and brushes, metal coatings and particles, and graphitic materials. We also review developments in the use of biophysical and computational methods for characterizing the structure of proteins at solution–solid interfaces. These approaches have provided important new insights into the physico-chemical factors that control protein conformation in near-surface environments, which represents a critical step towards the rational design of biotic–abiotic interfaces in biomedical and biotechnological applications. Graphical abstract Image 1 Highlights • The mechanistic understanding of protein unfolding on surfaces remains incomplete. • Lack of understanding has hindered the use of materials in biological environments. • Review highlights advances in elucidating impact of materials on protein structure. • Recent findings show lack of consistent observations between different systems. • Protein unfolding on surfaces may be confounded by various types of heterogeneities. [ABSTRACT FROM AUTHOR]

Abstract: Multimetallic clusters have long been investigated as molecular surrogates for reactive sites on metal surfaces. In the case of the μ4‐nitrido cluster [Fe4(μ4‐N)(CO)12]−, this analogy is limited owing to the electron‐withdrawing effect of carbonyl ligands on the iron nitride core. Described here is the synthesis and reactivity of [Fe4(μ4‐N)(CO)8(CNArMes2)4]−, an electron‐rich analogue of [Fe4(μ4‐N)(CO)12]−, where the interstitial nitride displays significant nucleophilicity. This characteristic enables rational expansion with main‐group and transition‐metal centers to yield unsaturated sites. The resulting clusters display surface‐like reactivity through coordination‐sphere‐dependent atom rearrangement and metal–metal cooperativity. [ABSTRACT FROM AUTHOR]

In this work we present a model for the surface oxide film growth considering the influence of space charge. The space charge field Esp is assumed proportional to the charge of moving metal ions and electrons in the oxide layer. The surface charge field Eox decreases as the Cabrera and Motts’ oxide thickness X grows to its limit X1 (Eox = VM/X). Eox remains constant for further growth of the oxide film (Eox = VM/X1). The obtained equation for the growing rate of the oxide film covers two stages. The first stage is characterized by a negligible space charge and is described by the typical inverse logarithmic law. During transition from thin to thick film, the oxidation growth rate is described by a direct logarithmic law which is confirmed by many experiments. At the end of this stage, the drift of metal ions is replaced by their diffusion that leads to parabolic law. [ABSTRACT FROM AUTHOR]

Most traditional techniques to recover latent fingermarks from metallic surfaces do not consider the metal surface properties and instead focus on the fingermark chemistry. The scanning Kelvin probe (SKP) technique is a non-contact, non-destructive method, used under ambient conditions, which can be utilised to recover latent prints from metallic surfaces and does not require any enhancement techniques or prevent subsequent forensic analysis. Where a fingermark ridge contacted the metal, the contact potential difference (CPD) contrast between the background surface and the fingermark contact area was 10-50mV. Measurements were performed on the untreated brass, nickel-coated brass and copper metal surfaces and compared to traditional forensic enhancement techniques such as Vacuum Metal Deposition (VMD) using Au-Zn and Au-Ag. Using VMD, the CPD change ranged from 0 to 150mV between the dissimilar metal surfaces affected by the fingermark. In general, SKP worked best without additional enhancement techniques. Scanning Electron Microscope (SEM) scans were used to identify the fingermark contact areas through a sodium, chlorine and oxygen electron probe micro-analyzer (EPMA). The fingermark was observed in the backscattered electron image as the carbon deposits scattered the electrons less than the surrounding metal surface. The fingermark is shown clearly in a Cathodoluminescence scan on the copper sample as it blocks the photon emission at band gap (2.17eV) from the underlying copper oxide (Cu2O) surface. For the first time, SEM, EPMA and Cathodoluminescence techniques were compared to SKP data. Visible and latent fingermarks were tested with latent, eccrinous fingermarks more easily imaged by SKP. Results obtained were very encouraging and suggest that the scanning Kelvin probe technique, which does not need vacuum, could have a place as a first stage analysis tool in serious crime investigation. [ABSTRACT FROM AUTHOR]

There is an increased interest in incorporating multi-wall carbon nanotubes (MWCNTs) into polymer matrices to control the adhesion of bacteria to surfaces and the subsequent formation of biofilm growth on the surface of water pipes, food packages, and medical devices. Microbial interactions with carbon nanotube-polymer composites in the environment are not well understood. The growth of Pseudomonas fluorescens (gram-negative) and Mycobacterium smegmatis (gram-positive) biofilms on copper, polyethylene (PE), polyvinyl chloride, and stainless steel was compared with growth on MWCNT-PE composites in order to gain insight into the effect of the surface properties of nanomaterials on the attachment and proliferation of microorganism which could result in the engineering of better, non-fouling materials. A statistical analysis of the biofilm growth showed a significant impact of materials for both P . fluorescens ( p  < 0.0001) and M . smegmatis ( p  = 0.00426). Biofilm growth after 56 days on PE compared to biofilm growth on copper surfaces decreased by 46.4% and 34.9% for P . fluorescens and M . smegmatis , respectively. Biofilm growth on PE-multiwall-carbon-nanotubes (MWCNTs)-composites surface compared to PE decreased by 89.3% and 29% for P . fluorescens and M . smegmatis , respectively. Bacterial species ( p  < 0.0006) and surface roughness ( p  < 0.0001) were important factors in determining the attachment and initial biofilm growth rate. The interactions between cells and material surface could be attributed to the complicated and collective effect of electrostatic forces, hydrophobic interactions, and hydrogen/covalent bonding. Further study is needed to determine whether or not there is a difference between the cell attachment in the exponential growth phase and the stationary, or decay, phase cells. [ABSTRACT FROM AUTHOR]

Abstract Atomic hydrogen is a highly reactive species of interest because of its role in a wide range of applications and technologies. Knowledge about the interactions of incident H atoms on metal surfaces is important for our understanding of many processes such as those occurring in plasma-enhanced catalysis and nuclear fusion in tokamak reactors. Herein we review some of the numerous experimental surface science studies that have focused on the interactions of H atoms that are incident on low-Miller index metal single-crystal surfaces. We briefly summarize the different incident H atom reaction mechanisms and several of the available methods to create H atoms in UHV environments before addressing the key thermodynamic and kinetic data available on metal and modified metal surfaces. Generally, H atoms are very reactive and exhibit high sticking coefficients even on metals where H 2 molecules do not dissociate under UHV conditions. This reactivity is often reduced by adsorbates on the surface, which also create new reaction pathways. Abstraction of surface-bound D(H) adatoms by incident H(D) atoms often occurs by an Eley-Rideal mechanism, while a hot atom mechanism produces structural effects in the abstraction rates and forms homonuclear products. Additionally, incident H atoms can often induce surface reconstructions and populate subsurface and bulk absorption sites. The absorbed H atoms recombine to desorb H 2 at lower temperature and can also exhibit higher subsequent reactivity with adsorbates than surface-bound H adatoms. Incident H atoms, either directly or via sorbed hydrogen species, hydrogenate adsorbed hydrocarbons, sulfur, alkali metals, oxygen, halogens, and other adatoms and small molecules. Thus, H atoms from the gas phase incident on surfaces and adsorbed layers create new reaction channels and products beyond those found from interactions of H 2 molecules. Detailed aspects of the dynamics and energy transfer associated with these interactions and the important applications of hydrogen in plasma processing of semiconductors are beyond the scope of this review. [ABSTRACT FROM AUTHOR]

This paper presents a review of the experimental and theoretical investigations of halogen interaction with metal surfaces. The emphasis was placed on the recent measurements performed with a scanning tunneling microscope in combination with density functional theory calculations. The surface structures formed on metal surface after halogen interaction are classified into three groups: chemisorbed monolayer, surface halide, bulk-like halide. Formation of monolayer structures is described in terms of surface phase transitions. Surface halide phases are considered to be intermediates between chemisorbed halogen and bulk halide. The modern theoretical approaches in studying the dynamics of metal halogenation reactions are also presented. [ABSTRACT FROM AUTHOR]

The aim of this study was to analyze the impact of hydrodynamic forces on the multiplication ofE. coli, and biofilm formation and dispersion. The experiments were provided in a flow chamber simulating a cleaning-in-place system. Biofilm biomass was measured using a crystal violet dye method. The results show that hydrodynamic forces affect not only biofilm formation and dispersion but the multiplication ofE. coliin the first place. We found more biofilm biomass on the rough surface than on the smooth one. The results of the biofilm formation test show that laminar flow promotes the biofilm growth over 72 h, meanwhile turbulent flow after 48 h causes decrease in biomass. The results of the biofilm dispersion test, in contrast, show that laminar flow removed less biofilm from both materials that turbulent flow did. Therefore, taking into account these findings in cleaning-in-place technology can substantially reduceE. colimultiplication and biofilm formation. [ABSTRACT FROM PUBLISHER]

The effect that the ionizing radiation caused by radioactive contamination of soil exerts on the surface of carbon steel 20 samples, on their corrosion resistance, and on operation reliability according to lowcycle fatigue tests (taking into account that fatigue is one of the main causes of failures resulting from corrosion and mechanical damage of thin-wall metal structures, in particular, of pipelines) was studied. It was shown that even low activity levels (below maximum permissible levels) caused corrosion loss of the metal and a decrease in the operation reliability. Synergistic protective compounds suppressing the destructive radiation effects and ensuring reliable operation of metal structures due to chelation of the surface metal atoms were developed using computer simulation. [ABSTRACT FROM AUTHOR]

Depth profiling using surface sensitive analysis methods in combination with sputter ion etching is a common procedure for thorough material investigations, where clean surfaces free of any contamination are essential. Hence, surface analytic studies are mostly performed under ultra-high vacuum (UHV) conditions, but the cleanness of such UHV environments is usually overrated. Consequently, the current study highlights the in principle known impact of the residual gas on metal surfaces (Fe, Mg, Al, Cr and Zn) for various surface analytics methods, like X-ray photoelectron spectroscopy (XPS), Auger electron spectroscopy (AES) and low-energy ion scattering (LEIS). The investigations with modern, state-of-the-art equipment showed different behaviors for the metal surfaces in UHV during acquisition: (i) no impact for Zn, even after long time, (ii) solely adsorption of oxygen for Fe, slight and slow changes for Cr and (iii) adsorption accompanied by oxide formation for Al and Mg. The efficiency of different counter measures was tested and the acquired knowledge was finally used for ZnMgAl coated steel to obtain accurate depth profiles, which exhibited before serious artifacts when data acquisition was performed in an inconsiderate way. [ABSTRACT FROM AUTHOR]

Chirality is a property of matter which manifests at any length scale and can equally appear as quantum phenomena and in three-dimensional macroscopic structures. However, while chirality can be easily achieved by removing the inversion symmetry operation in hexagonal or tetragonal metal structures, chirality in metals is an unusual and barely developed phenomenon. Nevertheless, chirality can greatly alter mechanical and functional features of materials, making them suitable for catalysis, optics, electromagnetism, thermoelectricity and superconductivity; properties strictly dependent on the anisotropy of the crystal and on the direction of the applied force. This review aims to extend the definition of chirality to describe nanoclusters, metal surfaces and crystals and to provide an interdisciplinary overview on how symmetry can affect their properties. This review was submitted as part of the 2016 Materials Literature Review Prize of the Institute of Materials, Minerals and Mining run by the Editorial Board of MST. Sponsorship of the prize by TWI Ltd is gratefully acknowledged. [ABSTRACT FROM AUTHOR]

The energetics at organic-metal interfaces are, to large extend, determined by the structure of the molecular adsorbate on the substrate surface. As shown by low-energy electron diffraction (LEED) the zigzag shape of picene leads to a peculiar monolayer structure on Ag(111), Ag(110), and Cu(111) with one molecule in the unit cell lying essentially flat and the other one adopting an edge-on orientation. The adsorbate-substrate coupling is weak as shown by ultraviolet photoelectron spectroscopy (UPS). This is in striking contrast to monolayers of straight pentacene, where all molecules lie flat and are strongly coupled, involving charge transfer complex formation on most of these surfaces. The peculiar packing structure of picene leads to weak interfacial coupling on clean metal surfaces. In contrast, pentacene is chemisorbed on Ag and Cu surfaces involving electron transfer from the substrate. [ABSTRACT FROM AUTHOR]

• Dopant atoms enhanced the adsorption behavior of benzene. • The highest adsorption energy was found in Pt 2 Pd 2 -Ag configuration AB. • A remarkable change from physisorption to chemisorption binding for benzene molecule. Heterogeneous catalysis, molecular sensors, and photovoltaics all rely on the interfaces between organic molecules and metal surfaces. Here, we study the adsorption of benzene on Ag(100) surface doped by Au n , Pd n , Pt n (n = 1–4), Au 2 Pd 2 , Au 2 Pt 2 and Pd 2 Pt 2 using density-functional theory (DFT), with the inclusion of van der Waals interactions, and compare with available computational and experimental result. The calculated quantities reveal that the interaction strength of Benzene with the surface gradually increases when it is doped by Pd or Pt atoms, showing a change in the nature of the interaction, from physisorption to chemisorption. We found that with surface allowing, one can tune the interaction strength. The charge transfer was found to occur from the molecule to the clean and doped surfaces with Au atoms and from the doped surface with Pd to the molecule. The redistribution of charge density indicates modifications in the features of the interface between the doped Ag(100) surfaces and benzene. In addition, alloying the Ag(100) surface with reactive TM changes substantially its electronic properties, which impacts its interactions with benzene. Finally, mixing two dopants or more can tune the electronic structure in designing more effective interfaces for various applications. [Display omitted] [ABSTRACT FROM AUTHOR]

Charge transfer interactions between C 60 and the metal surfaces of Ag(111), Cu(111), Au(111) and Pt(111) have been studied using synchrotron-based photoemission, resonant photoemission and X-ray absorption spectroscopies. By placing the X-ray absorption and valence band spectra on a common binding energy scale, the energetic overlap of the unoccupied molecular orbitals with the density of states of the underlying metal surface have been assessed in the context of possible charge transfer pathways. Resonant photoemission and resonant Auger data, measuring the valence region as a function of photon energy for C 60 adsorbed on Au(111) reveals three constant high kinetic energy features associated with Auger-like core-hole decay involving an electron transferred from the surface to the LUMO of the molecule and electrons from the three highest occupied molecular orbitals, respectively and in the presence of ultra-fast charge transfer of the originally photoexcited molecule to the surface. Data for the C 60 /Ag(111) surface reveals an additional Auger-like feature arising from a core-hole decay process involving more than one electron transferred from the surface into the LUMO. An analysis of the relative abundance of these core-hole decay channels estimates that on average 2.4 ± 0.3 electrons are transferred from the Ag(111) surface into the LUMO. A core-hole clock analysis has also been applied to assess the charge transfer coupling in the other direction, from the molecule to the Au(111) and Ag(111) surfaces. Resonant photoemission and resonant Auger data for C 60 molecules adsorbed on the Pt(111) and Cu(111) surfaces are shown to exhibit no super-Auger features, which is attributed to the strong modification of the unoccupied molecular orbitals arising from stronger chemical coupling of the molecule to the surface. [ABSTRACT FROM AUTHOR]

Water and its fragments are present on metal surfaces under all but the most extreme conditions, acting both as a reactive species and as a ligand in ways that have yet to be fully explored. This review focuses on experimental studies of the chemical species and hydrogen bonding structures that form in the first layer adsorbed on a metal surface. The development of non-invasive probes that avoid dissociating water, or disrupting fragile bonding structures, now allows experiments to distinguish between different structural models for water and its fragments at the surface, allowing us to test the accuracy of modern structural calculations and provide a better picture of how the metal surface influences the structures and chemical species present. We start by describing the behaviour of Pt(1 1 1), whose redox chemistry is important in electrochemical fuel cells and has been studied in detail, providing a good reference system against which to discuss the effect changing the surface symmetry and metal reactivity has on the interface structure. Evidence for the presence and the role of hydroxyl and hydrated ‘hydronium’ species is described and we discuss the outlook for future experiments and identify some questions that remain to be resolved. [ABSTRACT FROM PUBLISHER]

We study the effect of electron and phonon degrees of freedom on the relaxation dynamics of adsorption processes in gas-surface systems by using ab initio molecular dynamics that incorporates an electronic friction force (AIMDEF). As representative cases we have chosen three systems with different adsorption energies and adsorbate-to-surface atom mass ratios: H on Pd(1 0 0), N on Ag(1 1 1), and N 2 on Fe(1 1 0). We show, through inspection of the total energies and trajectories of the hot adsorbates on the surface, that electron–hole (e–h) pair excitations dominate relaxation of the light gas species, while the phonon channel is dominant for the heavy species. In the latter case e–h pairs become more important at the final thermalization stages. [ABSTRACT FROM AUTHOR]

Bacterial adhesion can be dictated by different surface characteristics. In this study we concentrate on the surface roughness of a stainless steel material. We prepared the stainless steel surfaces by 3D polishing, brushing, grinding and electropolishing. Untreated stainless steel surfaces were also considered. The corresponding surface roughness was assessed by profilometry and atomic force microscopy. In experiments we have used different types of bacteria. The rate of adhered bacteria on metal surfaces was determined spectrophotometrically. The results showed that the rate of adhered bacteria increases with increasing surface roughness. Scanning electron microscopy was used to image surfaces in order to determine locations of adhered bacteria. The increased adhesion of bacteria on more rough surfaces results from an increased interplay between the increasing effective surface area and increasing numbers of cracks, voids and gaps. [ABSTRACT FROM AUTHOR]

Visual appearance of an object significantly influences a consumer's choice and largely controls the market economy. The perceived quality of products is governed by surface's optical properties (reflection, refraction, etc.), geometrical properties (roughness, waviness, etc.), and chemical properties (oxide layer formation, thermal variation, etc.). Surface shininess attracts researchers from many different disciplines, in particular manufacturing, metrology, psychology, physiology, and computer science. Unfortunately, there are still huge knowledge gaps on characterizing and appraising shiny surfaces in a reproducible way. This paper introduces the main definitions and physics of shininess and gloss, methods of gloss sensing, and relates these definitions and methods to surface generation by grinding. Automated gloss measurement is difficult in particular for free-form surfaces, and optical quality is still often evaluated by human workers. Gloss models are often based on the bidirectional reflection distribution function (BRDF) of the surface, but the models are commonly not connected with the manufacturing process. This study proposes to consider the geometrical features (defects, waviness, lay, and roughness) of metal surfaces as well as the physical and chemical features (grain structure and microlayers) to understand surface appearance and manufacturing in a holistic way. Preliminary tests show that 2D roughness measurements are not connected well with measured gloss units (GUs) and subjective, perceived quality. More fundamental research on the generation and measurement of surface appearance is needed and would benefit many industries. [ABSTRACT FROM AUTHOR]

In this article, we propose a Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic quantum dynamics at metal surfaces with a continuous spectrum. This method consists of a Monte-Carlo algorithm for sampling the initial wave packets on the phase space and a surface-hopping type stochastic time propagation scheme for the wave packets. We prove that to reach a certain accuracy threshold, the sample size required is independent of both the semiclassical parameter ε and the number of metal orbitals N , which makes it one of the most promising methods to study the nonadiabatic dynamics. The algorithm and its convergence properties are also validated numerically. Furthermore, we carry out numerical experiments including exploring the nuclei dynamics, electron transfer and finite-temperature effects, and demonstrate that our method captures the physics which can not be captured by classical surface hopping trajectories. • An efficient Frozen Gaussian Sampling (FGS) algorithm for simulating nonadiabatic dynamics at metal surfaces is proposed. • The sample size required is independent of the number of orbitals N and the semiclassical parameter ε. • FGS algorithm can capture the physics that classical surface hopping trajectories fail to capture. [ABSTRACT FROM AUTHOR]

Possible adsorbate induced reconstruction effects of methanethiolate (MeS) and methaneselenolate (MeSe) on Au(111) are studied employing density functional theory (DFT). For the purposes of this study these simple alkanechalcogenates prove to be representative models for chalcogenate molecules with larger rest groups. MeS and MeSe show very similar properties regarding the adsorption at the unreconstructed and reconstructed surfaces. The latter are constructed by systematically introducing defects at various adsorbate coverages. It turns out that only if the defect site is occupied by at least two molecules the costs of creating the defect can be counterbalanced by the energetic gain and thus adsorbate induced reconstruction gets energetically feasible. Furthermore, for various molecular coverages the adatom-dichalcogenate model, as found by Maksymovych et al. (Phys. Rev. Lett. 97 (2006) 146103), is indeed the most stable reconstruction motif among the simple models studied herein. In order to mimic the impact of the environment, e.g. solvent effects, temperature or electric potentials, the stability of the reconstruction motifs was studied as a function of both the chemical potential of the adsorbate and the energy needed to create the defect substrate structure following the ansatz of ab initio atomistic thermodynamics. This approach hints at the fact that different reconstruction motifs can be realized in different chemical environments. [ABSTRACT FROM AUTHOR]

We review several representative experimental results of action spectroscopy (AS) of single molecules on metal surfaces using a scanning tunneling microscope (STM) by M. Kawai’s group over last decade. The experimental procedures to observe STM-AS are described. A brief description of a low-temperature STM and experimental setup are followed by key experimental techniques of how to determine an onset bias voltage of a reaction and how to measure a current change associated with reactions and finally how to observe AS for single molecule reactions. The experimental results are presented for vibrationally mediated chemical transformation of trans -2-butene to 1.3-butadiene molecule and rotational motion of a single cis -2-butene molecule among four equivalent orientations on Pd(1 1 0). The AS obtained from the motion clearly detects more vibrational modes than inelastic electron tunneling spectroscopy with an STM. AS is demonstrated as a useful and novel single molecule vibrational spectroscopy. The AS for a lateral hopping of water dimer on Pt(1 1 1) is presented as an example of novelty. Several distinct vibrational modes are detected as the thresholds in the AS. The assignment of the vibrational modes determined from the analysis of the AS is made from a view of the adsorption geometry of hydrogen-bond donor or acceptor molecules in water dimer. A generic theory of STM-AS, i.e., a reaction rate or yield as a function of bias voltage, is presented using a single adsorbate resonance model for single molecule reactions induced by the inelastic tunneling current. Formulas for the reaction rate R ( V ) and Y ( V ) , i.e., reaction yield per electron Y ( V ) = eR ( V ) / I are derived. It provides a versatile framework to analyze any vibrationally mediated reactions of single adsorbates on metal surfaces. Numerical examples are presented to demonstrate generic features of the vibrational generation rate and Y ( V ) at different levels of approximations and to show how the effective broadening of the vibrational density of states (as described by Gaussian or Lorentzian functions) manifest themselves in Y ( V ) near the threshold bias voltage corresponding to a vibrational excitation responsible for reactions. A prefactor of Y ( V ) is explicitly derived for various types of elementary processes. Our generic formula of Y ( V ) also underlines the need to observe Y ( V ) at both bias voltage polarities, which can provide additional insight into the adsorbate projected density of states near the Fermi level within a span of the vibrational energy. The theory is applied to analysis of some highlights of the experimental results: Xe transfer, hopping of a single CO molecule on Pd(1 1 0), a dissociation of a single dimethyl disulfide (CH 3 S) 2 and a hopping of a dissociated product, i.e., single methyl thiolate CH 3 S on Cu(1 1 1). It underlines that an observation of Y ( V ) at both bias polarities permits us to certain insight into the molecular alignment with respect to the Fermi level. [ABSTRACT FROM AUTHOR]

Graphene, a two-dimensional (2D) material with unique electronic properties, appears to be an ideal object for the application of surface-science methods. Among them, a family of scanning probe microscopy methods (STM, AFM, KPFM) and the corresponding spectroscopy add-ons provide information about the structure and electronic properties of graphene on the local scale (from [ABSTRACT FROM AUTHOR]

Silicene is emerging as a two-dimensional material with very attractive electronic properties for a wide range of applications; it is a particularly promising material for nano-electronics in silicon-based technology. Over the last decade, the existence and stability of silicene has been the subject of much debate. Theoretical studies were the first to predict a puckered honeycomb structure with electronic properties resembling those of graphene. Though these studies were for free-standing silicene, experimental fabrication of silicene has been achieved so far only through epitaxial growth on crystalline surfaces. Indeed, it was only in 2010 that researchers presented the first experimental evidence of the formation of silicene on Ag(1 1 0) and Ag(1 1 1), which has launched silicene in a similar way to graphene. This very active field has naturally led to the recent growth of silicene on Ir(1 1 1), ZrB 2 (0 0 0 1) and Au(1 1 0) substrates. However, the electronic properties of epitaxially grown silicene on metal surfaces are influenced by the strong silicene–metal interactions. This has prompted experimental studies of the growth of multi-layer silicene, though the nature of its “silicene” structure remains questionable. Of course, like graphene, synthesizing free-standing silicene represents the ultimate challenge. A first step towards this has been reported recently through chemical exfoliation from calcium disilicide (CaSi 2 ). In this review, we discuss the experimental and theoretical studies of silicene performed to date. Special attention is given to different experimental studies of the electronic properties of silicene on metal substrates. New avenues for the growth of silicene on other substrates with different chemical characteristics are presented along with foreseeable applications such as nano-devices and novel batteries. [ABSTRACT FROM AUTHOR]

Enhanced colors can be formed when white light is irradiated on the surface ripples induced by femtosecond laser. In this paper, we have demonstrated the ability to display the diverse colors by simultaneously adjusting the incident white light angle and the ripples orientation. Furthermore, our investigation revealed that multi-patterns constituted by ripples with different orientations could be designed on metal surfaces. The diverse display for the desired ones can be realized by exquisitely varying the incident light angle and rotating sample angle. More interestingly, it is found that, although the same patterns could be displayed under different conditions, the colors might be different. These findings can provide a novel method to carry and identify high quantity of information, which may find potential applications in the fields of information storage, identifying codes and anti-counterfeiting patterns. [ABSTRACT FROM AUTHOR]

Carbon monoxide is a ubiquitous molecule in surface science, materials chemistry, catalysis and nanotechnology. Its interaction with a number of metal surfaces is at the heart of major processes, such as Fischer-Tropsch synthesis or fuel-cell optimization. Recent works, coupling structural and nanoscale in situ analytic tools have highlighted the ability of metal surfaces and nanoparticles to undergo restructuring after exposure to CO under fairly mild conditions, generating nanostructures. This Minireview proposes a brief overview of recent examples of such nanostructuring, which leads to a discussion about the driving force in reversible and non-reversible situations. [ABSTRACT FROM AUTHOR]

An inspection of mechanically damaged areas on manufactured metal parts is necessary to produce high-quality products. A scanning probe on a sample is necessary for a conventional surface inspection system, which is time-consuming. We propose a novel high-speed detection method for defects on metal surfaces with rolling indentations. To obtain a large field of view in a measurement, we used a laser sheet that was expanded with a laser line generator and also used an expanded collimated beam, rather than a small laser spot as used in conventional techniques. Furthermore, we used an obliquely incident laser beam to suppress the effect of the rolling indentations surrounding defects, and also applied spatial frequency filtering to extract only defects. The spatial frequency filtering under oblique incidence is theoretically explained and defect extraction was investigated in experiments. [ABSTRACT FROM AUTHOR]

Highlights: [•] Bond breaking of general RO–H organic compounds on various metal surfaces. [•] Brønsted–Evans–Polanyi like relationships for the O–H bond break in organics. [•] Activation energy for the O–H bond break versus adsorption energy of the products. [•] Mean absolute error for the BEP is 0.13eV. [•] Good agreement between estimated and calculated data for a test set. [ABSTRACT FROM AUTHOR]

Abstract: In this work, we have investigated the surface structure of Cu3Au(001) using low energy electron diffraction analysis and ab initio calculations by density functional theory. Our results indicate a different structure from that usually reported in the literature, where we have observed a stacking fault between the first and third layers of the surface. The rippling effect and the interlayer distances belonging to the first six layers of the surface were calculated and compared with other works too. Specifically, a rippling with gold atoms moving towards the vacuum in the first layer of 0.09Å was observed and of 0.02Å in the third layer. A small expansion of the first interlayer distance of 1.3% and a contraction of 0.8% at the second also were observed. Finally, ab initio calculations performed in this work are in good agreement with the experimental results. [Copyright &y& Elsevier]

We validate a computational setup based on density functional theory to investigate hexagonal boron nitride ( h-BN) monolayers grown on different transition metals exposing hexagonal surfaces. An extended assessment of our approach for the characterization of the geometrical and electronic structure of such systems is performed. Due to the lattice mismatch with the substrate, the monolayers can form Moiré-type superstructures with very long periodicities on the surface. Thus, proper models of these interfaces require very large simulation cells (more than 1,000 atoms) and an accurate description of interactions that are modulated with the specific registry of h-BN on the metal. We demonstrate that efficient and accurate calculations can be performed in such large systems using Gaussian basis sets and dispersion corrections to the (semi-)local density functionals. Four different metallic substrates, Rh(111), Ru(0001), Cu(111), and Ni(111), are explicitly considered, and the results are compared with previous experimental and computational studies. [ABSTRACT FROM AUTHOR]

We demonstrate that reflectance difference spectroscopy (RDS) is sensitive to defects induced by ion bombardment, located either in the topmost layer or in the subsurface region. Most importantly, these two kinds of defects can be spectrally discriminated, since the corresponding signatures in the RD spectrum arise from perturbations of different types of electronic states: The defects in the topmost surface layer mainly lead to a quenching of the optical anisotropy related to surface states, whereas the subsurface defects strongly affect the optical anisotropy originating from transitions between surface-modified bulk electronic states. Consequently, RDS can be used to simultaneously monitor the defects in the topmost surface layer and in the subsurface region in-situ during ion bombardment and thermal annealing. [ABSTRACT FROM AUTHOR]

Abstract: In this paper we present a combined low-energy electron diffraction (LEED) and a DFT study of the Au(110)c(2×2)–Sb surface in order to determine its atomic structure. The DFT calculations, using both LDA and GGA approaches, have indicated that the adsorption of antimony atoms on the Au(110) surface hollow sites is energetically more favored as compared with other possible adsorption sites. The LEED analysis also showed a Sb-overlayer termination with the Sb atoms segregating to the hollow sites instead of forming an Au–Sb surface alloy. This overlayer results to be contracted of about 0.16Å with the first gold layer presenting a small expansion (0.04Å) with respect to the Au bulk interlayers distance. The agreement between the LEED and DFT results is very good. [Copyright &y& Elsevier]

Abstract: Silicene–the silicon-based counterpart of graphene–has a two dimensional structure that is responsible for the variety of potentially useful chemical and physical properties. The existence of silicene has been achieved recently owing to experiments involving epitaxial growth of silicon as stripes on Ag(001), ribbons on Ag(110), and sheets on Ag(111). The nano-ribbons observed on Ag(110) were found–by both high definition experimental scanning tunneling microscopy images and density functional theory calculations–to consist of an arched honeycomb structure. Angle resolved photo-emission experiments on these silicene nano-ribbons on Ag(110), along the direction of the ribbons, showed a band structure which is analogous to the Dirac cones of graphene. Unlike silicon surfaces, which are highly reactive to oxygen, the silicene nano-ribbons were found to be resistant to oxygen reactivity. On the theoretical side, recent extensive efforts have been deployed to understand the properties of standalone silicene sheets and nano-ribbons using both tight-binding and density functional theory calculations. Unlike graphene it is demonstrated that silicene sheets are stable only if a small buckling (0.44 Å) is present. The electronic properties of silicene nano-ribbons and silicene sheets were found to resemble those of graphene. Although this is a fairly new avenue, the already obtained outcome from these important first steps in understanding silicene showed promising features that could give a new future to silicon in the electronics industry, thus opening a promising route toward wide-range applications. In this review, we plan to introduce silicene by presenting the available experimental and theoretical studies performed to date, and suggest future directions to be explored to make the synthesis of silicene a viable one. [Copyright &y& Elsevier]

Abstract: In this work we report on a very accurate low-energy electron diffraction (LEED) and a DFT study of Au(110)-(1×2) in order to determine its surface geometry. The LEED results indicate a surface missing row reconstruction with a large contraction of , a pairing in the second layer and in the fourth layer , and a buckling in the third layer of 0.30Å and in the fifth layer of 0.01Å. These LEED results are in very good agreement with those found by the DFT calculations. [Copyright &y& Elsevier]

Abstract: We present vibrational dynamics and thermodynamics for the (100) surfaces of Cu, Ag, Pd, Pt and Au using a real space approach. The force field for these systems is described by density functional theory. The changes in the vibrational dynamics and thermodynamics from those in bulk are confined mostly to the first-layer. A substantial enhancement of the low-frequency end of the acoustic branch was found and is related to a loosening of the bond at the surface. The thermodynamics of the first-layer also show significant differences (higher heat capacity, lower free energy and higher mean vibrational square amplitudes) from what obtains in bulk. Comparing these results with those calculated using embedded-atom method potentials, we discovered that for Ag(100) and Cu(100), the two methods yield very similar results while for Pd(100), Pt(100) and Au(100) there are substantial differences. [Copyright &y& Elsevier]