Atomistic Perspective Research Articles

The role of halide ions in the anisotropic growth of gold nanoparticles: a microscopic, atomistic perspective.

We provide a microscopic view of the role of halides in controlling the anisotropic growth of gold nanorods through a combined computational and experimental study. Atomistic molecular dynamics simulations unveil that Br(-) adsorption is not only responsible for surface passivation, but also acts as the driving force for CTAB micelle adsorption and stabilization on the gold surface in a facet-dependent way. The partial replacement of Br(-) by Cl(-) decreases the difference between facets and the surfactant density. Finally, in the CTAC solution, no halides or micellar structures protect the gold surface and further gold reduction should be uniformly possible. Experimentally observed nanoparticle's growth in different CTAB/CTAC mixtures is more uniform and faster as the amount of Cl(-) increases, confirming the picture from the simulations. In addition, the surfactant layer thickness measured on nanorods exposed to CTAB and CTAC quantitatively agrees with the simulation results.

Professionalism in action – Music teachers on an assessment journey

The points of departure in this article are questions regarding assessment in music education. These are related to issues of professional responsibility and accountability as well as a holistic view on education as conceptualized in Deweyean pragmatism and concern the risk of criteria compliance. A participatory action research project in a Swedish Upper secondary school focusing on assessment of music is presented, where the purpose of the research was to develop knowledge about music teachers’ experience and conceptualizations regarding assessment practices within the frame of the National Arts Programme. This is enabled by asking the following research questions: In what ways do teachers conceptualize musical knowledge and learning and educational communication in relation to assessment? What qualities appear within the teachers’ conceptualizations regarding knowledge, learning, communication and assessment of students’ knowledge? Aims from the field of praxis were integrated in the project, with focus on equivalent assessment and legal certainty. Results from the research project show the music teachers’ ability to shift between atomistic and holistic perspectives but at the same time keep their holistic view of assessment and learning. Equivalence is according to the teachers something different than uniformity, and is only possible through reflection and collaboration, internally as well as externally with other practitioners.

Mechanical response of low stacking fault energy Co–Ni alloys – Continuum, mesoscopic and atomic level treatments

Low stacking fault energy fcc alloys deform via either mechanical twinning or dislocation slip. A single crystal poses an excellent avenue to studying inherent material preference for plastic flow mechanism. This paper examines the physical process underlying the flow behavior of Co-33%Ni single crystals at continuum, mesoscale and atomic levels. Digital image correlation, electron backscatter diffraction and transmission electron microscopy permitted an in-depth analysis of the deformed microstructure. Emphasis is placed on rationalizing the experimentally discovered competing modes of plasticity from an atomistic perspective. Experimentally, predisposition for slip or twinning is observed to be specific to a given crystal orientation and loading direction (tension/compression). Particularly, flow in 〈111〉tension and 〈100〉compression proceeds with a single twinning system and ensuing twin-slip interactions. By contrast, dislocation slip nucleation followed by multi-system forest hardening prevails in the post-yield behavior of 〈123〉tension and 〈111〉compression cases. The stress-strain curves reveal that the twinning-mediated flow induces superior hardening characterized by pronouncedly serrated flow behavior. A first principle based mechanics model is proffered to account for the relative material propensity for either slip or twinning on the basis of atomic level generalized stacking/planar fault energies. The model considers the energy balance between the applied work and the total energy expenses as contributed by both continuum and atomistic effects. Upon establishing the γ surfaces from density functional theory, critical stresses for the initiation of slip, twin and post-yield twin-slip interactions are computed within a Peierls-Nabarro modeling framework. Predicted critical stress levels demonstrate reasonably good agreement with the experimentally determined critical resolved shear stresses. Concurrence of the theoretical inferences with the experimental observations is discussed in the context of the related literature.

Bridging Thermodynamic and Kinetic Processes in Electrochemically Relevant Calculated Pourbaix Diagrams

Bridging Thermodynamic and Kinetic Processes in Electrochemically Relevant Calculated Pourbaix Diagrams Yolanda A. Small Abstract The transition states in kinetic processes are often experimentally elusive. Computational tools can be used to gain an atomistic perspective into these transition states. A learning tool to guide students through the complexities of the theory while gaining an appreciation for the coupling of thermodynamic and kinetic processes is explored here. A computational protocol which hinges on combining calculated free-energy profiles along proposed mechanistic pathways with electrochemically relevant Pourbaix diagrams has been proposed with the design of molecular catalysts for hydrogen production and oxidation in mind. Two experimentally characterized species are used to test the protocol; the outcome suggests interesting ways to tune a catalyst for optimal activity. This protocol can be used as either a pedagogical tool or a research directive on how to combine theoretical analysis to experimental electrochemical studies. Full Text: PDF DOI: 10.15640/jns.v3n2a3

Atomistic modeling of ion implantation technologies in silicon

Requirements for the manufacturing of electronic devices at the nanometric scale are becoming more and more demanding on each new technology node, driving the need for the fabrication of ultra-shallow junctions and finFET structures. Main implantation strategies, cluster and cold implants, are aimed to reduce the amount of end-of-range defects through substrate amorphization. During finFET doping the device body gets amorphized, and its regrowth is more problematic than in the case of conventional planar devices. Consequently, there is a renewed interest on the modeling of amorphization and recrystallization in the front-end processing of Si. We present multi-scale simulation schemes to model amorphization and recrystallization in Si from an atomistic perspective. Models are able to correctly predict damage formation, accumulation and regrowth, both in the ballistic and thermal-spike regimes, in very good agreement with conventional molecular dynamics techniques but at a much lower computational cost.

Effect of moisture on the mechanical properties of CFRP–wood composite: An experimental and atomistic investigation

Adhesive bonding of fiber-reinforced polymers (FRP) to wood has been proven as a general way to achieve reinforcement and rehabilitation for wood structures. Although a significant mechanical enhancement can be acquired by using such approach, there exists a big concern about the long-term performance of the FRP–wood composite, especially under the effect of moisture. In this paper, both experimental and atomistic approaches are adopted for investigating the moisture effect on the entire FRP–wood composite system. Macroscopic mechanical tests show that its mechanical properties and its fracture behaviors notably change at different levels of ambient humidity. From an atomistic perspective, molecular dynamics (MD) simulations reveal that water molecules significantly reduce the adhesion energy between wood and epoxy. Results from experimental and numerical studies imply that the strength of the FRP–wood interface critically determines the mechanical performance of the entire system. The water molecules absorbed at the interface are crucial to the durability of multi-layer systems and a general mechanism governing the failure modes of such systems is found.

Atomic mechanism of internal friction in a model metallic glass

Internal friction (IF) describes the ability of materials to damp out mechanical oscillations. It is a crucial engineering parameter and also conveys unique microscopic information about structural defects, transport phenomena, and phase transformations in solids. While IF predominately results from lattice defects in crystalline materials, the origin of IF remains unclear in disordered materials, like metallic glasses. In this paper, we study the atomic rearrangements that govern IF in a model metallic glass, via numerical simulations of dynamical mechanical spectroscopy together with structural analysis. We identify cooperative and avalanchelike thermal-driven excitations as an underlying mechanism and demonstrate a linearlike relation between the concentrations of these excitations and the values of IF. Structurally, these excitations can be hindered, and thus suppress IF, by slow atoms that usually associate with full icosahedral symmetry. Our results also provide practical guides in tuning IF in metallic glasses from atomistic perspectives.

L'analisi semiotica come ricerca empirica sul testo

Empirical research on texts has become a central issue for contemporary semiotics ever since its theorists shifted their methodological approach from signs, codes or languages to texts. The former Saussurian approach implied an atomistic perspective tending to discover grammmars regulating combinations of separate units. On the contrary, the semiotics of texts focuses on the complexity of its object. Text is meant as a syntagmatic cut-out of any socially meaningful phenomenon. How does one decide how wide a text’s boundaries may be? What are the criteria one is to employ to decide about its pertinence? Studying texts empirically should concentrate on how they are construed and chosen, relying on reader/consumer’s response, trying to understand readers’ interpretive work. Reception theory may help only in so far as it is modified by time transformations, by the change in reading models, and by becoming a public reception theory, which always yields a further text, and always implies a comparison between the original text and the one produced by the audience.

In-silico investigation of Rayleigh instability in ultra-thin copper nanowire in premelting regime

Motivated by the recent experimental reports, we explore the formation of Rayleigh-like instability in metallic nanowires during the solid state annealing, a concept originally introduced for liquid columns. Our molecular dynamics study using realistic interatomic potential reveals instability induced pattern formation at temperatures even below the melting temperature of the wire, in accordance with the experimental observations. We find that this is driven by the surface diffusion, which causes plastic slips in the system initiating necking in the nanowire. We further find the surface dominated mass-transport is of subdiffusive nature with time exponent less than unity. Our study provides an atomistic perspective of the instability formation in nanostructured solid phase.

Multiscale Simulation of Crack Propagation Based on Molecular Dynamics

A multiscale simulation approach is developed to investigate mechanism of crack propagation from the atomistic perspective. The finite elements (FE) method has been applied to obtain displacement load of the model. The quadrangle region around the crack tip crack tip has been prepared for the molecular dynamics (MD) model. The displacement load calculated by FE was applied to boundaries of the MD model. The simulation results show that the evolution of atomic configuration of the system includes dislocation emission, atomic disorder, atom bond rupture and microcrack propagation.

Atomic-scale analysis of liquid-gallium embrittlement of aluminum grain boundaries

Material strengthening and embrittlement are controlled by intrinsic interactions between defects, such as grain boundaries (GBs), and impurity atoms that alter the observed deformation and failure mechanisms in metals. In this work, we explore the role of atomistic-scale energetics on liquid-metal embrittlement of aluminum (Al) due to gallium (Ga). Ab initio and molecular mechanics were employed to probe the formation/binding energies of vacancies and segregation energies of Ga for 〈100〉, 〈110〉 and 〈111〉 symmetric tilt grain boundaries (STGBs) in Al. We found that the GB local arrangements and resulting structural units have a significant influence on the magnitude of the vacancy binding energies. For example, the mean vacancy binding energies for 〈100〉, 〈110〉 and 〈111〉 STGBs in the 1st layer was found to be −0.63, −0.26 and −0.60eV, respectively. However, some GBs exhibited vacancy binding energies closer to bulk values, indicating interfaces with zero sink strength, i.e. these GBs may not provide effective pathways for vacancy diffusion. The results from the present work showed that the GB structure and the associated free volume also play significant roles in Ga segregation and the subsequent embrittlement of Al. The Ga mean segregation energies for 〈100〉, 〈110〉 and 〈111〉 STGBs in the 1st layer were found to be −0.21, −0.09 and −0.21 eV, respectively, suggesting a stronger correlation between the GB structural unit, its free volume and the segregation behavior. Furthermore, as the GB free volume increased, the difference in segregation energies between the 1st layer and the 0th layer increased. Thus, the GB character and free volume provide an important key to understanding the degree of anisotropy in various systems. The overall characteristic Ga absorption length scale was found to be about ∼10, 8 and 12 layers for 〈100〉, 〈110〉 and 〈111〉 STGBs, respectively. In addition, a few GBs of different tilt axes with relatively high segregation energies (between 0 and −0.1eV) at the boundary were also found. This finding provides a new atomistic perspective for the GB engineering of materials with smart GB networks to mitigate or control liquid-metal embrittlement and more general embrittlement phenomena in alloys.

Tetrahexahedral Pt–Pd alloy nanocatalysts with high-index facets: an atomistic perspective on thermodynamic and shape stabilities

Metallic nanoparticles with high-index facets exhibit exceptional electrocatalytic activity owing to the high density of low coordination sites at the surface, thus they have attracted intense interest over the past few years. Alloying could further improve their catalytic activity by the synergy effects of high-index facets and electronic structures of components. Using atomistic simulations, we have investigated thermodynamic and shape stabilities of tetrahexahedral Pt–Pd alloy nanoparticles respectively bound by {210} and {310} facets. Energy minimization through Monte Carlo simulations has indicated that the outermost layer is predominated by Pd atoms while Pt atoms preferentially occupy the sub-outermost layer of nanoparticles. Molecular dynamics simulations of the heating process have shown that the {210} faceted nanoparticles possess better thermodynamic and shape stabilities than the {310} faceted ones. The coordination numbers of surface atoms were used to explore the potential origin of the different stabilities. Furthermore, a high Pt ratio will help enhance their stabilities. For both faceted nanoparticles, the melting has homogeneously developed from the surface into the core, and the tetrahexahedra have finally evolved into sphere-like shape prior to the overall melting. These results are helpful for understanding the composition and thermodynamic properties of high-index faceted nanoparticles, and are also of practical importance to the development of alloy nanocatalysts.

Single-crystalline and multiple-twinned gold nanoparticles: an atomistic perspective on structural and thermal stabilities

Morphologies of gold nanoparticles play an important role in determining their chemical and physical (catalytic, electronic, optical, etc.) properties. Therefore, a fundamental understanding of the morphological stability is of crucial importance to their applications. In this article, we employed atomistic simulations to systematically investigate the structural and thermal stabilities of gold particles with eight representative nanoshapes, including single-crystalline and multiple-twinned structures. Our investigation has revealed that the truncated octahedron and the octahedron possessed the best structural stability, while the tetrahedron and the icosahedron did the worst. Further analyses have discovered different thermal stabilities and diverse melting behaviors in these particles. Especially, an inhomogeneous melting of the icosahedron was disclosed, and the relevant mechanism was elucidated. This study provides significant insight not only into the experimental preparation of gold nanoparticles but also into the design of gold nanostructures with both high catalytic activity and excellent stability.

In SituSynchrotron X-Ray Diffraction Study of the Rhombohedral-to-HT-Cubic Phase Transformation in Ln6WO12(Ln = Y, Ho, Er, Yb)

The high-temperature rhombohedral-to-fcc phase transformation in the Ln6WO12 (Ln = Y, Ho, Er, Yb) system was investigated by thermal analysis and in situ X-ray diffraction. The process was characterized by thermodynamic, kinetic, and mechanistic criteria, and the role of the rare-earth cation on the transformation properties trends was evaluated. An atomistic perspective on the accompanying structural change is presented, as well as a characterization of the associated shape and volume changes. A twofold comparison is performed with the similar low-temperature fcc-to-rhombohedral transformation in the same system. One aspect contrasts the structural changes related to each process, manifested by the behavior of the lattice parameters and transformation characteristics. The second concerns the sequence of transformations according to composition and suggests the order of thermal stability of Ln polyhedra in each phase.

Molecular dynamics studies of thermal dissipation during shock induced spalling

Under shock loadings, the temperature of materials may vary dramatically during deformation and fracture processes. Thus, thermal effect is important for constructing dynamical failure models. Existing works on thermal dissipation effects are mostly from meso- to macro-scale levels based on phenomenological assumptions. The main purpose of the present work is to provide several atomistic scale perspectives about thermal dissipation during spall fracture by nonequilibrium molecular dynamics simulations on single-crystalline and nanocrystalline Pb. The simulations show that temperature arising starts from the vicinity of voids during spalling. The thermal dissipation rate in void nucleation stage is much higher than that in the later growth and coalescence stages. Both classical spallation and micro-spallation are taken into account. Classical spallation is corresponding to spallation phenomenon where materials keep in solid state during shock compression and release stages, while micro-spallation is corresponding to spallation phenomenon where melting occurs during shock compression and release stages. In classical spallation, whether residuary dislocations are produced in pre-spall stages has significant influences on thermal dissipation rate during void growth and coalescence. The thermal dissipation rates decrease as shock intensity increases. When the shock intensity exceeds the threshold of micro-spallation, the thermal dissipation rate in void nucleation stage drops precipitously. It is found that grain boundaries mainly influence the thermal dissipation rate in void nucleation stage in classical spallation. In micro-spallation, the grain boundary effects are insignificant.

First principles view on chemical compound space: Gaining rigorous atomistic control of molecular properties

AbstractA well‐defined notion of chemical compound space (CCS) is essential for gaining rigorous control of properties through variation of elemental composition and atomic configurations. Here, we give an introduction to an atomistic first principles perspective on CCS. First, CCS is discussed in terms of variational nuclear charges in the context of conceptual density functional and molecular grand‐canonical ensemble theory. Thereafter, we revisit the notion of compound pairs, related to each other via “alchemical” interpolations involving fractional nuclear charges in the electronic Hamiltonian. We address Taylor expansions in CCS, property nonlinearity, improved predictions using reference compound pairs, and the ounce‐of‐gold prize challenge to linearize CCS. Finally, we turn to machine learning of analytical structure property relationships in CCS. These relationships correspond to inferred, rather than derived through variational principle, solutions of the electronic Schrödinger equation. © 2013 Wiley Periodicals, Inc.

The energies of formation and mobilities of Cu surface species on Cu and ZnO in methanol and water gas shift atmospheres studied by DFT

Catalysts based on copper, such as the Cu/ZnO/Al2O3 system are widely used for industrial scale methanol synthesis and the low temperature water gas shift reaction. A common characteristic of these catalysts is that they deactivate quite rapidly during operation and therefore understanding their deactivation by sintering is highly relevant. In this work, we study the nature of the species that are responsible for transport of the Cu metal in this catalyst type using density functional theory calculations within a chemical potential formalism. The stability and mobility of Cu–X (Cu, OH, CO, CH3O, HCOO) species are investigated in relevant synthesis gas compositions. The CuCO and Cu2HCOO species are identified to be predominant for metal transport on Cu particles, which may contribute to sintering of Cu by particle migration and coalescence. Furthermore, transport of Cu on ZnO is found mostly to occur through CuCO species, which indicates that CuCO is an important species for Ostwald ripening in a Cu/ZnO catalyst. These results provide atomistic perspective on the diffusion of the species that may contribute to catalyst sintering, therefore lending a valuable foundation for future investigations of the stability of Cu catalysts.

Resolving the complex role of enzyme conformational dynamics in catalytic function

Despite growing evidence suggesting the importance of enzyme conformational dynamics (ECD) in catalysis, a consensus on how precisely ECD influences the chemical step and reaction rates is yet to be reached. Here, we characterize ECD in Cyclophilin A, a well-studied peptidyl-prolyl cis-trans isomerase, using normal and accelerated, atomistic molecular dynamics simulations. Kinetics and free energy landscape of the isomerization reaction in solution and enzyme are explored in unconstrained simulations by allowing significantly lower torsional barriers, but in no way compromising the atomistic description of the system or the explicit solvent. We reveal that the reaction dynamics is intricately coupled to enzymatic motions that span multiple timescales and the enzyme modes are selected based on the energy barrier of the chemical step. We show that Kramers' rate theory can be used to present a clear rationale of how ECD affects the reaction dynamics and catalytic rates. The effects of ECD can be incorporated into the effective diffusion coefficient, which we estimate to be about ten times slower in enzyme than in solution. ECD thereby alters the preexponential factor, effectively impeding the rate enhancement. From our analyses, the trend observed for lower torsional barriers can be extrapolated to actual isomerization barriers, allowing successful prediction of the speedup in rates in the presence of CypA, which is in notable agreement with experimental estimates. Our results further reaffirm transition state stabilization as the main effect in enhancing chemical rates and provide a unified view of ECD's role in catalysis from an atomistic perspective.

Evolutionary continuous cellular automaton for the simulation of wet etching of quartz

Anisotropic wet chemical etching of quartz is a bulk micromachining process for the fabrication of micro-electro-mechanical systems (MEMS), such as resonators and temperature sensors. Despite the success of the continuous cellular automaton for the simulation of wet etching of silicon, the simulation of the same process for quartz has received little attention—especially from an atomistic perspective—resulting in a lack of accurate modeling tools. This paper analyzes the crystallographic structure of the main surface orientations of quartz and proposes a novel classification of the surface atoms as well as an evolutionary algorithm to determine suitable values for the corresponding atomistic removal rates. Not only does the presented evolutionary continuous cellular automaton reproduce the correct macroscopic etch rate distribution for quartz hemispheres, but it is also capable of performing fast and accurate 3D simulations of MEMS structures. This is shown by several comparisons between simulated and experimental results and, in particular, by a detailed, quantitative comparison for an extensive collection of trench profiles.

Thickness of Hydroxyapatite Nanocrystal Controls Mechanical Properties of the Collagen–Hydroxyapatite Interface

Collagen-hydroxyapatite interfaces compose an important building block of bone structures. While it is known that the nanoscale structure of this elementary building block can affect the mechanical properties of bone, a systematic understanding of the effect of the geometry on the mechanical properties of this interface between protein and mineral is lacking. Here we study the effect of geometry, different crystal surfaces, and hydration on the mechanical properties of collagen-hydroxyapatite interfaces from an atomistic perspective, and discuss underlying deformation mechanisms. We find that the presence of hydroxyapatite significantly enhances the tensile modulus and strength compared with a tropocollagen molecule alone. The stiffening effect is strongly dependent on the thickness of the mineral crystal until a plateau is reached at 2 nm crystal thickness. We observe no significant differences due to the mineral surface (Ca surface vs OH surface) or due to the presence of water. Our result shows that the hydroxyapatite crystal with its thickness confined to the nanometer size efficiently increases the tensile modulus and strength of the collagen-hydroxyapatite composite, agreeing well with experimental observations that consistently show the existence of extremely thin mineral flakes in various types of bones. We also show that the collagen-hydroxyapatite interface can be modeled with an elastic network model which, based on the results of atomistic simulations, provides a good estimate of the surface energy and other mechanical features.