We have introduced a new class of stable organometallic Cr reagents (compounds 1–4) that are readily prepared, yet reactive enough to serve as precursors. They were used for ethylene tetramerization ...catalysis following stoichiometric activation by in situ protonation. This study highlights the importance of balancing stability with reactivity in generating an organometallic precursor that is useful in catalysis. Moreover, precursor 4 allowed for the isolation and crystallographic characterization of a room-temperature stable cationic species, (PNP)CrR2 + (R = o-C6H4(CH2)2OMe, PNP = i PrN(PPh2)2). This complex (5) may be used as a single component precatalyst, without any alkylaluminum reagents. This result provides an unprecedented level of insight into the kind of structures that must be produced from more complicated activation processes.
The nucleation and subsequent growth of helium bubbles in bulk tungsten is investigated using molecular dynamics simulations. By considering a setting that includes the diffusion process of helium ...clusters, we study their attachment to existing bubbles and their interaction with tungsten crowdion structures generated in the bubble growth process. We find that incoming helium atoms, and especially small helium clusters, can become trapped in the crowdion structures, providing nucleation sites for new helium bubbles, and leading to a distributed network of bubbles rather than a single, growing bubble. The nature of this network depends on both the temperature and the implantation flux of helium. Our results indicate that the kinetic interaction of He with generated dislocations is a key factor dictating the evolution of bubble distributions in plasma-exposed tungsten.
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The growth process of He bubbles in W is investigated using molecular dynamics and parallel replica dynamics for growth rates spanning 6 orders of magnitude. Fast and slow growth regimes are defined ...relative to typical diffusion hopping times of W interstitials around the He bubble. Slow growth rates allow the diffusion of interstitials around the bubble, favoring the biased growth of the bubble towards the surface. In contrast, at fast growth rates interstitials do not have time to diffuse around the bubble, leading to a more isotropic growth and increasing the surface damage.
The production of energy through nuclear fusion poses serious challenges related to the stability and performance of materials in extreme conditions. In particular, the constant bombardment of the ...walls of the reactor with high doses of He ions is known to lead to deleterious changes in their microstructures. These changes follow from the aggregation of He into bubbles that can grow and blister, potentially leading to the contamination of the plasma, or to the degradation of their mechanical properties. We computationally study the behavior of small clusters of He atoms in W in conditions relevant to fusion energy production. Using a wide range of techniques, we investigate the thermodynamics of the clusters and their kinetics in terms of diffusivity, growth, and breakup, as well as mutation into nanobubbles. Our study provides the essential ingredients to model the early stages of He exposure leading up to the nucleation of He bubbles.
Network Service Orchestration: A survey Saraiva de Sousa, Nathan F.; Lachos Perez, Danny A.; Rosa, Raphael V. ...
Computer communications,
06/2019, Letnik:
142-143
Journal Article
Recenzirano
Odprti dostop
Business models of network service providers are undergoing an evolving transformation fueled by vertical customer demands and technological advances such as 5G, Software Defined Networking (SDN), ...and Network Function Virtualization (NFV). Emerging scenarios call for agile network services consuming network, storage, and compute resources across heterogeneous infrastructures and administrative domains. Coordinating resource control and service creation across interconnected domains and diverse technologies becomes a grand challenge. Research and development efforts are being devoted to enabling orchestration processes to automate, coordinate, and manage the deployment and operation of network services. In this survey, we delve into the topic of Network Service Orchestration (NSO) by reviewing the historical background, relevant research projects, enabling technologies, and standardization activities. We define key concepts and propose a taxonomy of NSO approaches and solutions to pave the way towards a common understanding of the various ongoing efforts around the realization of diverse NSO application scenarios. Based on the analysis of the state of affairs, we present a series of open challenges and research opportunities, altogether contributing to a timely and comprehensive survey on the vibrant and strategic topic of network service orchestration.
The atomic stick-slip behavior of a Pt tip sliding on a Au(111) surface is studied with atomic force microscopy (AFM) experiments and accelerated (i.e., reduced sliding speed) molecular dynamics (MD) ...simulations. The MD and AFM conditions are controlled to match, as closely as possible, the geometry and orientation, load, temperature, and compliance. We observe clear stick-slip without any damage. Comparison of both MD and AFM results with the thermally activated Prandtl-Tomlinson model shows that MD results at the highest speeds are not in the thermally activated regime. At lower speeds, within the thermally activated regime, AFM and MD provide consistent energetics, but attempt frequencies differ by orders of magnitude. Because this discrepancy lies in attempt frequencies and not energetics, atomistic details in MD simulations can be reliably used in interpreting AFM data if the MD speeds are slow enough.
Rare-earth and actinide complexes are critical for a wealth of clean-energy applications. Three-dimensional (3D) structural generation and prediction for these organometallic systems remains a ...challenge, limiting opportunities for computational chemical discovery. Here, we introduce Architector, a high-throughput in-silico synthesis code for s-, p-, d-, and f-block mononuclear organometallic complexes capable of capturing nearly the full diversity of the known experimental chemical space. Beyond known chemical space, Architector performs in-silico design of new complexes including any chemically accessible metal-ligand combinations. Architector leverages metal-center symmetry, interatomic force fields, and tight binding methods to build many possible 3D conformers from minimal 2D inputs including metal oxidation and spin state. Over a set of more than 6,000 x-ray diffraction (XRD)-determined complexes spanning the periodic table, we demonstrate quantitative agreement between Architector-predicted and experimentally observed structures. Further, we demonstrate out-of-the box conformer generation and energetic rankings of non-minimum energy conformers produced from Architector, which are critical for exploring potential energy surfaces and training force fields. Overall, Architector represents a transformative step towards cross-periodic table computational design of metal complex chemistry.
Stochastic dynamics, such as molecular dynamics, are important in many scientific applications. However, summarizing and analyzing the results of such simulations is often challenging due to the high ...dimension in which simulations are carried out and, consequently, due to the very large amount of data that are typically generated. Coarse graining is a popular technique for addressing this problem by providing compact and expressive representations. Coarse graining, however, potentially comes at the cost of accuracy, as dynamical information is, in general, lost when projecting the problem in a lower-dimensional space. This article shows how to eliminate coarse-graining error using two key ideas. First, we represent coarse-grained dynamics as a Markov renewal process. Second, we outline a data-driven, non-parametric Mori–Zwanzig approach for computing jump times of the renewal process. Numerical tests on a small protein illustrate the method.
Molecular dynamics (MD) is one of the most widely used techniques in computational materials science. By providing fully resolved trajectories, it allows for a natural description of static, ...thermodynamic, and kinetic properties. A major hurdle that has hampered the use of MD is the fact that the timescales that can be directly simulated are very limited, even when using massively parallel computers. In this study, we compare two time-parallelization approaches, parallel replica dynamics (ParRep) and parallel trajectory splicing (ParSplice), that were specifically designed to address this issue for rare event systems by leveraging parallel computing resources. Using simulations of the relaxation of small disordered platinum nanoparticles, a comparative performance analysis of the two methods is presented. The results show that ParSplice can significantly outperform ParRep in the common case where the trajectory remains trapped for a long time within a region of configuration space but makes rapid structural transitions within this region.
A notable impediment in maintaining high electric fields in accelerating structures is the onset of breakdown events. While bulk mechanical properties of the materials are known to significantly ...affect the breakdown propensity, the underlying mechanisms coupling electric fields to bulk plastic deformation in experimentally relevant thermal and electrical loading conditions remain to be identified at the atomic scale. We present the results of large-scale molecular dynamics simulations (MD) to investigate a possible mode of coupling. Specifically, we consider the activation of Frank-Read sources, which leads to dislocation multiplication, under the combined action of biaxial thermal stresses caused by rf losses and surface tractions induced by electric fields. With the help of a charge-equilibration formalism incorporated in a classical MD model, we show that the creation of surface slipped steps can couple to electric fields in a way that enhances local stresses and facilitates further activation of existing dislocation sources. We quantify the possible enhancement of surface slip under typical microstructural parameters of annealed copper. We show that such a mechanism could potentially promote breakdown precursor formation at very high electric fields, but that its impact is limited at fields typical of the operation of accelerator structures. In this regime, thermal stresses caused by rf losses are expected to be the main drivers of plastic deformation.
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