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At least 1,603 records · Page 89

Experimental demonstration of necessary conditions for X-ray induced synthesis of cesium superoxide

Absorption of sufficiently energetic X-ray photons by a molecular system results in a cascade of ultrafast electronic relaxation processes which leads to a distortion and dissociation of its molecular structure. Here, in this work, we demonstrate that only decomposition of powdered cesium oxalate monohydrate induced by monochromatic X-ray irradiation under high pressure leads to the formation of cesium superoxide. Whereas, for an unhydrated form of cesium oxalate subjected to the same extreme conditions, only degradation of the electron density distribution is observed. Moreover, the corresponding model of X-ray induced electronic relaxation cascades with an emphasis on water molecules’ critical role is proposed. Our experimental results suggest that the presence of water molecules in initially solid-state systems (i.e. additional electronic relaxation channels) together with applied high pressure (reduced interatomic/intermolecular distance) could potentially be a universal criteria for chemical and structural synthesis of novel compounds via X-ray induced photochemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catlas: an automated framework for catalyst discovery demonstrated for direct syngas conversion

Catalyst discovery is paramount to support access to energy and key chemical feedstocks in a post fossil fuel era. Exhaustive computational searches of large material design spaces using ab initio methods like density functional theory (DFT) are infeasible. We seek to explore large design spaces at relatively low computational cost by leveraging large, generalized, graph-based machine learning (ML) models, which are pretrained and therefore require no upfront data collection or training. We present Catlas, a framework that distributes and automates the generation of adsorbate-surface configurations and ML inference of DFT energies to achieve this goal. Catlas is open source, making ML assisted catalyst screenings easy and available to all. To demonstrate its efficacy, we use Catlas to explore catalyst candidates for the direct conversion of syngas to multi-carbon oxygenates. For this case study, we explore 947 stable/metastable binary, transition metal intermetallics as possible catalyst candidates. On this subset of materials, we are able to predict the adsorption energy of key descriptors, *CO and *OH, with good accuracy (0.16, 0.14 eV MAE, respectively). Using the projected selectivity towards C 2+ oxygenates from an existing microkinetic model, we identified 144 candidate materials. For 10 promising candidates, DFT calculations reveal a good correlation with our assessment using ML. Finally, among the top elemental combinations were Pt–Ti, Pd–V, Ni–Nb, and Ti–Zn, all of which appear unexplored experimentally.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Catalytic production of tetrahydropyran (THP): a biomass-derived, economically competitive solvent with demonstrated use in plastic dissolution

Tetrahydropyran (THP) is a five-carbon heterocyclic ether that is non-carcinogenic, non-peroxide forming, biodegradable, and economically competitive with tetrahydrofuran (THF) as a solvent. In this work, THP has been synthesized from renewable biomass at >99.8% selectivity and 98% yield via hydrogenation of furfural-derived 3,4-dihydropyran (DHP) over Ni/SiO 2 in a continuous flow reactor at 150–200 °C. The apparent activation energy of THP formation is 31 kJ mol -1 , and the reaction orders with respect to the partial pressures of H 2 , DHP, and THP are: 2, 1, and -0.3. The kinetic data has been fitted to a Hougen–Watson model where the rate limiting step is the hydrogenation of adsorbed DHP. Ni/SiO 2 is shown to have a low deactivation rate constant of 0.012 h -1 over 100 h time on stream and can be regenerated in situ. As a performance advantage, THP is shown to be resistant to ring opening polymerization under strongly acidic conditions that THF is not, revealing it to be a superior solvent. Further, the minimum selling price of THP is competitive with the market price of THF ($$900 – 1400 per ton ) at a DHP feedstock cost of $1000 per ton. Conductor-like Screening Model for Real Solvents (COSMO-RS) and molecular dynamics (MD) simulations with 1008 solvents and 8 common plastics have demonstrated that THP can serve as an alternative solvent to THF, 2-methyltetrahydrofuran (MeTHF), and cyclopentyl methyl ether (CPME) for plastic dissolution, especially low-density polyethylene (LDPE), polypropylene (PP), polystyrene (PS) and polyvinyl chloride (PVC). This work establishes THP as a green solvent with excellent thermal, chemical and peroxidative stability that can be used for numerous applications, including waste plastic recycling.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Demonstrating a butylamine-based deconstruction method for poplar biomass and conversion by diverse microbial strains

Low-boiling alkylamines such as butylamine offer promise as effective biomass pretreatment solvents that can be readily recovered and recycled; however, their capability to support microbial conversion of nutrients present in hydrolysates represents an important area for investigation. Here we employed butylamine to pretreat poplar biomass and characterize its effects on the release of fermentable sugars after solvent removal and enzymatic hydrolysis, as well as the biocompatibility of the produced hydrolysates with three organisms commonly used as bioconversion hosts. We observed that residual butylamine and the derivative butylacetamide were present in high enough concentrations to exert toxicity to strains of Aspergillus niger, Pseudomonas putida, and Rhodosporidium toruloides that produce malic acid, isoprenol and bisabolene, respectively. Removal of the toxic compounds by charcoal filtration and nutrient supplementation resulted in a hydrolysate containing >100 g L −1 of sugars that enabled strong growth, substrate consumption and bioproduct accumulation, outperforming defined cultivation media. This is the first demonstration of a butylamine-based deconstruction process for poplar biomass at a pilot-scale to achieve conversion of high sugar concentrations to valuable bioproducts with engineered microbes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

ATLAS HL-LHC Demonstrators with Data Carousel: Dataon-Demand and Tape Smart Writing

The High Luminosity upgrade to the LHC (HL-LHC) is expected to deliver scientific data at the multi-exabyte scale. To tackle this unprecedented data storage challenge, the ATLAS experiment initiated the Data Carousel project in 2018. Data Carousel is a tape-driven workflow in which bulk production campaigns with input data resident on tape are executed by staging and promptly processing a sliding window to disk buffer such that only a small fraction of inputs are pinned on disk at any one time. Put in ATLAS production before Run3, Data Carousel continues to be our focus for seeking new opportunities in disk space savings, and enhancing tape usage throughout the ATLAS Distributed Computing (ADC) environment. These efforts are highlighted by two recent ATLAS HL-LHC demonstrator projects: data-on-demand and tape smart writing. In this paper, we will discuss the recent studies and outcomes from these projects. The research was conducted together with site experts at CERN and Tier-1 centers.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Eddy current NDE performance demonstrations using simulation tools

To carry out performance demonstrations of the Eddy-Current NDE processes applied on French nuclear power plants, EDF studies the possibility of using simulation tools as an alternative to measurements on steam generator tube mocks-up. This paper focuses on the strategy led by EDF to assess and use code{sub C}armel3D and Civa, on the case of Eddy-Current NDE on wears problem which may appear in the U-shape region of steam generator tubes due to the rubbing of anti-vibration bars.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Optoelectronic measurement of x-ray synchrotron pulses: A proof of concept demonstration

Optoelectronic detection using photoconductive coplanar stripline devices has been applied to measuring the time profile of x-ray synchrotron pulses, a proof of concept demonstration that may lead to improved time-resolved x-ray studies. Laser sampling of current vs time delay between 12 keV x-ray and 800 nm laser pulses reveal the {approx}50 ps x-ray pulse width convoluted with the {approx}200 ps lifetime of the conduction band carriers. For GaAs implanted with 8 MeV protons, a time profile closer to the x-ray pulse width is observed. The protons create defects over the entire depth sampled by the x-rays, trapping the x-ray excited conduction electrons and minimizing lifetime broadening of the electrical excitation.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Demonstration of achromatic cold-neutron microscope utilizing axisymmetric focusing mirrors

An achromatic cold-neutron microscope with magnification 4 is demonstrated. The image-forming optics is composed of nested coaxial mirrors of full figures of revolution, so-called Wolter optics. The spatial resolution, field of view, and depth of focus are measured and found consistent with ray-tracing simulations. Methods of increasing the resolution and magnification are discussed, as well as the scientific case for the neutron microscope. In contrast to traditional pinhole-camera neutron imaging, the resolution of the microscope is determined by the mirrors rather than by the collimation of the beam, leading to possible dramatic improvements in the signal rate and resolution.

43 PARTICLE ACCELERATORS↗

Feasibility study of endoscopic x-ray luminescence computed tomography: Simulation demonstration and phantom application

Even though endoscopic fluorescence diffuse optical tomography (eFDOT) exhibits significant potential, currently its application is limited due to the existence of strong autofluorescence and the imaging inaccuracy caused by a very short source-detector distance. Motivated by the emerging X-ray luminescence computed tomography (XLCT) technology, we presented an endoscopic XLCT (eXLCT) methodology. In the methodology, the aperture angle of the objective was incorporated into the forward model, providing a more accurate description of light propagation. Numerical simulation with a heterogeneous geometry and an imaging experiment with a physical phantom were illustrated to demonstrate the feasibility of the presented eXLCT methodology.

36 MATERIALS SCIENCE↗

Demonstrating 1 nm-oxide-equivalent-thickness HfO{sub 2}/InSb structure with unpinning Fermi level and low gate leakage current density

In this work, the band alignment, interface, and electrical characteristics of HfO{sub 2}/InSb metal-oxide-semiconductor structure have been investigated. By using x-ray photoelectron spectroscopy analysis, the conduction band offset of 1.78 ± 0.1 eV and valence band offset of 3.35 ± 0.1 eV have been extracted. The transmission electron microscopy analysis has shown that HfO{sub 2} layer would be a good diffusion barrier for InSb. As a result, 1 nm equivalent-oxide-thickness in the 4 nm HfO{sub 2}/InSb structure has been demonstrated with unpinning Fermi level and low leakage current of 10{sup −4} A/cm{sup −2}. The D{sub it} value of smaller than 10{sup 12} eV{sup −1}cm{sup −2} has been obtained using conduction method.

36 MATERIALS SCIENCE↗

Experimental demonstration of mode-selective phonon excitation of 6H-SiC by a mid-infrared laser with anti-Stokes Raman scattering spectroscopy

Mode-selective phonon excitation by a mid-infrared laser (MIR-FEL) is demonstrated via anti-Stokes Raman scattering measurements of 6H-silicon carbide (SiC). Irradiation of SiC with MIR-FEL and a Nd-YAG laser at 14 K produced a peak where the Raman shift corresponds to a photon energy of 119 meV (10.4 μm). This phenomenon is induced by mode-selective phonon excitation through the irradiation of MIR-FEL, whose photon energy corresponds to the photon-absorption of a particular phonon mode.

36 MATERIALS SCIENCE↗

First demonstration of an asymmetric kinetic equilibrium for a thin current sheet

The modeling of steady state collisionless asymmetric tangential current layers is a challenging and poorly understood problem. For decades now, this difficulty has been limiting numerical models to approximate equilibria built with locally Maxwellian current layers and theoretical analyses to the very restricted Harris equilibrium. We show how the use of any distribution functions depending only on local macroscopic quantities results in a strong alteration of the current layer internal structure, which converges toward an unpredictable quasi-steady state with emission of ion scale perturbations. This transient can be explained in terms of ion kinetic and electron fluid physics. We demonstrate, for the first time, the validity of an asymmetric kinetic equilibrium model as well as its usability as an initial condition of hybrid kinetic simulations. This offers broad perspectives for the current sheet modeling, for which the early phase of instabilities can be studied within the kinetic formalism.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Interaction of Sr-90 with site candidate soil for demonstration disposal facility at Serpong

Interaction of radiostrontium (Sr-90) with site candidate soil for demonstration disposal facility to be constructed in the near future at Serpong has been done. This activity is to anticipate the interim storage facility at Serpong nuclear area becomes full off condition, and show to the public how radioactive waste can be well managed with the existing technology. To ensure that the location is save, a reliability study of site candidate soil becomes very importance to be conducted through some experiments consisted some affected parameters such as contact time, effect of ionic strength, and effect of Sr{sup +} ion in solution. Radiostrontium was used as a tracer on the experiments and has role as radionuclide reference in low-level radioactive waste due to its long half-live and it's easy to associate with organism in nature. So, interaction of radiostrontium and soil samples from site becomes important to be studied. Experiment was performed in batch method, and soil sample-solution containing radionuclide was mixed in a 20 ml of PE vial. Ratio of solid: liquid was 10{sup −2} g/ml. Objective of the experiment is to collect the specific characteristics data of radionuclide sorption onto soil from site candidate. Distribution coefficient value was used as indicator where the amount of initial and final activities of radiostrontium in solution was compared. Result showed that equilibrium condition was reached after contact time 10 days with Kd values ranged from 1600-2350 ml/g. Increased in ionic strength in solution made decreased of Kd value into soil sample due to competition of background salt and radiostrontium into soil samples, and increased in Sr ion in solution caused decreased of Kd value in soil sample due to limitation of sorption capacity in soil samples. Fast condition in saturated of metal ion into soil samples was reached due to a simple reaction was occurred.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental and theoretical demonstration of acoustic Bloch oscillations in porous silicon structures

We report the theoretical calculations and the experimental demonstration of acoustic Bloch oscillations and Wannier-Stark ladders in linear tilted multilayer structures based on porous silicon. The considered structures consist of layers with constant porosity alternated by layers with a linear gradient in the parameter η=1/v{sub L}{sup 2} along the growth direction in order to tilt the acoustic band gap. The purpose of this gradient is to mimic the tilted electronic miniband structure of a superlattice semiconductor under an external electric field. In this way, acoustic Wannier-Stark ladders of equidistant modes are formed and they were experimentally confirmed in the transmission spectrum around 1.2 GHz. Their frequency separation defines the period of the acoustic Bloch oscillations. We fabricated three different structures with the same thicknesses but different values in the η parameter to observe the effect on the period of the Bloch oscillations. We measured the acoustic transmission spectra in the frequency domain, and by using the Fourier transform, we obtained the transmission in the time domain. The transmission spectra of the fabricated samples show acoustic Bloch oscillations with periods of 27, 24, and 19 ns. The experimental results are in good agreement with the transfer matrix calculations. The observed phenomenon is the acoustic counterpart of the well known electronic Bloch oscillations.

36 MATERIALS SCIENCE↗

Constructing polyatomic potential energy surfaces by interpolating diabatic Hamiltonian matrices with demonstration on green fluorescent protein chromophore

Simulating molecular dynamics directly on quantum chemically obtained potential energy surfaces is generally time consuming. The cost becomes overwhelming especially when excited state dynamics is aimed with multiple electronic states. The interpolated potential has been suggested as a remedy for the cost issue in various simulation settings ranging from fast gas phase reactions of small molecules to relatively slow condensed phase dynamics with complex surrounding. Here, we present a scheme for interpolating multiple electronic surfaces of a relatively large molecule, with an intention of applying it to studying nonadiabatic behaviors. The scheme starts with adiabatic potential information and its diabatic transformation, both of which can be readily obtained, in principle, with quantum chemical calculations. The adiabatic energies and their derivatives on each interpolation center are combined with the derivative coupling vectors to generate the corresponding diabatic Hamiltonian and its derivatives, and they are subsequently adopted in producing a globally defined diabatic Hamiltonian function. As a demonstration, we employ the scheme to build an interpolated Hamiltonian of a relatively large chromophore, para-hydroxybenzylidene imidazolinone, in reference to its all-atom analytical surface model. We show that the interpolation is indeed reliable enough to reproduce important features of the reference surface model, such as its adiabatic energies and derivative couplings. In addition, nonadiabatic surface hopping simulations with interpolation yield population transfer dynamics that is well in accord with the result generated with the reference analytic surface. With these, we conclude by suggesting that the interpolation of diabatic Hamiltonians will be applicable for studying nonadiabatic behaviors of sizeable molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Experimental demonstration of ultrasensitive sensing with terahertz metamaterial absorbers: A comparison with the metasurfaces

Planar metasurfaces and plasmonic resonators have shown great promise for sensing applications across the electromagnetic domain ranging from the microwaves to the optical frequencies. However, these sensors suffer from lower figure of merit and sensitivity due to the radiative and the non-radiative loss channels in the plasmonic metamaterial systems. We demonstrate a metamaterial absorber based ultrasensitive sensing scheme at the terahertz frequencies with significantly enhanced sensitivity and an order of magnitude higher figure of merit compared to planar metasurfaces. Magnetic and electric resonant field enhancement in the impedance matched absorber cavity enables stronger interaction with the dielectric analyte. This finding opens up opportunities for perfect metamaterial absorbers to be applied as efficient sensors in the finger print region of the electromagnetic spectrum with several organic, explosive, and bio-molecules that have unique spectral signature at the terahertz frequencies.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Demonstration of a GaAs-based 1550-nm continuous wave photomixer

An Er:GaAs-based 1550-nm CW photomixer is demonstrated. The related mechanism is extrinsic photoconductivity with optical absorption between the localized deep levels created by the Er and the extended states above the conduction band edge of GaAs. With the power boost made possible by a fiber-coupled erbium-doped-fiber amplifier, the Er:GaAs photomixers, operating at 1550 nm, radiate THz power levels easily measured by a Golay cell, and display a power spectrum having a −3 dB roll-off frequency of 307 GHz. This corresponds to a photocarrier lifetime of 520 fs, in good agreement with a previous measurement of the bandwidth of the same material in a photoconductive switch.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗