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Creators/Authors contains: "Minor, Andrew M"

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  1. C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials. 
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  2. C–H bond activation enables the facile synthesis of new chemicals. While C–H activation in short-chain alkanes has been widely investigated, it remains largely unexplored for long-chain organic molecules. Here, we report light-driven C–H activation in complex organic materials mediated by 2D transition metal dichalcogenides (TMDCs) and the resultant solid-state synthesis of luminescent carbon dots in a spatially-resolved fashion. We unravel the efficient H adsorption and a lowered energy barrier of C–C coupling mediated by 2D TMDCs to promote C–H activation and carbon dots synthesis. Our results shed light on 2D materials for C–H activation in organic compounds for applications in organic chemistry, environmental remediation, and photonic materials. 
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  3. Single-phase body-centered cubic (bcc) refractory medium- or high-entropy alloys can retain compressive strength at elevated temperatures but suffer from extremely low tensile ductility and fracture toughness. We examined the strength and fracture toughness of a bcc refractory alloy, NbTaTiHf, from 77 to 1473 kelvin. This alloy’s behavior differed from that of comparable systems by having fracture toughness over 253 MPa·m1/2, which we attribute to a dynamic competition between screw and edge dislocations in controlling the plasticity at a crack tip. Whereas the glide and intersection of screw and mixed dislocations promotes strain hardening controlling uniform deformation, the coordinated slip of <111> edge dislocations with {110} and {112} glide planes prolongs nonuniform strain through formation of kink bands. These bands suppress strain hardening by reorienting microscale bands of the crystal along directions of higher resolved shear stress and continually nucleate to accommodate localized strain and distribute damage away from a crack tip. 
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  4. Plasmonic cathodes, whose nanoscale features may locally enhance optical energy from the driving laser trapped at the vacuum interface, have emerged as a promising technology for improving the brightness of metal cathodes. A six orders of magnitude improvement [1] in the non-linear yield of metals has been experimentally demonstrated through this type of nanopatterning. Further, nanoscale lens structures may focus light below its free-space wavelength offering multiphoton photoemission from a region near 10 times smaller [2] than that achievable in typical photoinjectors. In this proceeding, we report on our efforts to characterize the brightness of two plasmonic cathode concepts: a spiral lens and a nanogroove array. We demonstrate an ability to engineer and fabricate nanoscale patterned cathodes by comparing their optical properties with those computed with a finite difference time domain (FDTD) code. The emittance and nonlinear yield of the cathodes are measured under ultrafast laser irradiation. Finally, prospects of this technology for the control and acceleration of charged particle beams are discussed. 
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  5. Abstract The abrupt occurrence of twinning when Mg is deformed leads to a highly anisotropic response, making it too unreliable for structural use and too unpredictable for observation. Here, we describe an in-situ transmission electron microscopy experiment on Mg crystals with strategically designed geometries for visualization of a long-proposed but unverified twinning mechanism. Combining with atomistic simulations and topological analysis, we conclude that twin nucleation occurs through a pure-shuffle mechanism that requires prismatic-basal transformations. Also, we verified a crystal geometry dependent twin growth mechanism, that is the early-stage growth associated with instability of plasticity flow, which can be dominated either by slower movement of prismatic-basal boundary steps, or by faster glide-shuffle along the twinning plane. The fundamental understanding of twinning provides a pathway to understand deformation from a scientific standpoint and the microstructure design principles to engineer metals with enhanced behavior from a technological standpoint. 
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  6. Abstract Corrosion is a ubiquitous failure mode of materials. Often, the progression of localized corrosion is accompanied by the evolution of porosity in materials previously reported to be either three-dimensional or two-dimensional. However, using new tools and analysis techniques, we have realized that a more localized form of corrosion, which we call 1D wormhole corrosion, has previously been miscategorized in some situations. Using electron tomography, we show multiple examples of this 1D and percolating morphology. To understand the origin of this mechanism in a Ni-Cr alloy corroded by molten salt, we combined energy-filtered four-dimensional scanning transmission electron microscopy and ab initio density functional theory calculations to develop a vacancy mapping method with nanometer-resolution, identifying a remarkably high vacancy concentration in the diffusion-induced grain boundary migration zone, up to 100 times the equilibrium value at the melting point. Deciphering the origins of 1D corrosion is an important step towards designing structural materials with enhanced corrosion resistance. 
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  7. Electron microscopy is uniquely suited for atomic-resolution imaging of heterogeneous and complex materials, where composition, physical, and electronic structure need to be analyzed simultaneously. Historically, the technique has demonstrated optimal performance at room temperature, since practical aspects such as vibration, drift, and contamination limit exploration at extreme temperature regimes. Conversely, quantum materials that exhibit exotic physical properties directly tied to the quantum mechanical nature of electrons are best studied (and often only exist) at extremely low temperatures. As a result, emergent phenomena, such as superconductivity, are typically studied using scanning probe-based techniques that can provide exquisite structural and electronic characterization, but are necessarily limited to surfaces. In this article, we focus not on the various methods that have been used to examine quantum materials at extremely low temperatures, but on what could be accomplished in the field of quantum materials if the power of electron microscopy to provide structural analysis at the atomic scale was extended to extremely low temperatures. 
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  8. null (Ed.)