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At least 253 records · Page 14

Metastable‐State Photoacids with Fast Reverse Reactions

Metastable-state photoacid (mPAH) has become a common tool for controlling and driving chemical processes with light. mPAHs with fast reverse reactions are desirable for precise temporal control or generating quick pulses of proton concentration. Here, in this work, different approaches towards fast reversing mPAHs are studied. Experimental and computational results showed that stabilizing the charge–transfer intermediate is an effective way to increase the rate. A novel mPAH with a reverse reaction ≈500 times faster than the most used mPAH in methanol is developed. Another water-soluble mPAH showed a reverse reaction with a rate constant of 7.8 s −1 , which is the fastest ever reported. The half-life of the acidic state is calculated to be 89 ms, which allowed to demonstrate sub-second switching using this mPAH.

Abbood, Rana [Florida Institute of Technology, Mel↗

A generic method for interfacing IEDs using low voltage interfaces to real-time simulators with hardware in the loop

This study presents an interface method (IM) to interconnect real-time simulators (RTSs) without amplifiers for different intelligent electronic devices (IEDs), such as protective relays, smart meters, and other devices. It is a significant topic for the power systems protection community because there are many protection devices with different requirements. These protection devices have pinouts that measure bus voltages/currents and breaker pole states and generate trip/close pulse signals. Most of the emulation test beds with RTSs and HIL need amplifiers to connect IEDs from different product manufacturers because the low-voltage interface levels are not available in some instruction manuals. Additionally, commercial amplifiers have cutoff frequency limitations and have an excessive cost when several IEDs are wired onto test beds. Then, the validation of protection and control systems with RTSs and IEDs in the loop from different vendors without amplifiers results in an unfeasible alternative. In this paper, the IM was based on using an interface box, power source, and RTS to identify IED inputs/outputs. Here, the sequence to recognize IED pinouts and calculate the current/voltage scaling factors is described. The IM was validated satisfactorily with RTS and a protection device (with unknown pinouts) in the loop.

42 ENGINEERING↗

Reactions of hydrazine with the amidogen radical and atomic hydrogen

The rate coefficient k 1 for NH 2 + N 2 H 4 was measured to be (5.4 ± 0.4) × 10 –14 cm 3 molecule –1 s –1 at 296 K. NH 2 was generated by pulsed laser photolysis of NH 3 at 193 nm, and monitored as a function of time by pulsed laser-induced fluorescence excited at 570.3 nm under pseudo-first order conditions in the presence of excess N 2 H 4 in an Ar bath gas. This reaction was also investigated computationally, with geometries and scaled frequencies obtained with M06-2X/6-311+G(2df,2p) theory, and single-point energies from CCSD(T)-F12b/cc-pVTZ-F12 theory, plus a term to correct approximately for electron correlation through CCSDT(Q). Three connected transition states are involved and rate constants were obtained via Multistructural Improved Canonical Variational Transition State Theory with Small Curvature Tunneling. Combination of experiment and theory leads to a recommended rate coefficient for hydrogen abstraction of k 1 = 6.3 × 10 –23 T 3.44 exp(+289 K/T) cm 3 molecule –1 s –1 . The minor channel for H + N 2 H 4 forming NH 2 + NH 3 was characterized computationally as well, to yield 5.0 × 10 –19 T 2.07 exp(-4032 K/T) cm 3 molecule –1 s –1 . Finally, these results are compared to several discordant prior estimates, and are employed in an overall mechanism to compare with measurements of half-lives of hydrazine in a shock tube.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure and dynamics of magneto-inertial, differentially rotating laboratory plasmas

We present a detailed characterization of the structure and evolution of differentially rotating plasmas driven on the MAGPIE pulsed-power generator (1.4 MA peak current, 240 ns rise time). The experiments were designed to simulate physics relevant to accretion discs and jets on laboratory scales. A cylindrical aluminium wire array Z pinch enclosed by return posts with an overall azimuthal off-set angle was driven to produce ablation plasma flows that propagate inwards in a slightly off-radial trajectory, injecting mass, angular momentum and confining ram pressure to a rotating plasma column on the axis. However, the plasma is free to expand axially, forming a collimated, differentially rotating axial jet that propagates at ${\approx }100\,{\rm km}\,{\rm s}^{-1}$ . The density profile of the jet corresponds to a dense shell surrounding a low-density core, which is consistent with the centrifugal barrier effect being sustained along the jet's propagation. We show analytically that, as the rotating plasma accretes mass, conservation of mass and momentum implies plasma radial growth scaling as $r \propto t^{1/3}$ . As the characteristic moment of inertia increases, the rotation velocity is predicted to decrease and settle on a characteristic value ${\approx }20\,{\rm km}\,{\rm s}^{-1}$ . We find that both predictions are in agreement with Thomson scattering and optical self-emission imaging measurements.

Valenzuela-Villaseca, V. (ORCID:0000000167721441)↗

Combined Effects of Hemicolligation and Ion Pairing on Reduction Potentials of Biphenyl Radical Cations

Here, formal reduction potentials of highly oxidizing and short-lived radical cations of substituted biphenyls generated by pulse radiolysis in 1,2-dichloroethane (DCE) were measured using a redox equilibrium ladder method. The effect of halide ion–radical interactions on reduction potentials of biphenyls was examined by utilizing the ability of DCE to release Cl – in the vicinity of the radical cation. The Hammett correlation of measured potentials across a range of over 700 mV shows saturation at high Hammett sigma values. This effect has been explained by both ion-pairing and hemicolligation interactions between biphenyl radical cations and Cl – and appears to modulate reduction potentials by as much as 400 mV. This finding offers a convenient way to manipulate the energetics of electron transfer involving organic redox species.

14 SOLAR ENERGY↗

Electronic Coherence and Coherent Dephasing in the Optical Control of Electrons in Graphene

Electronic coherence is of utmost importance for the access and control of quantum-mechanical solid-state properties. Using a purely electronic observable, the photocurrent, we measure a lower bound of the electronic coherence time of 22 ± 4 fs in graphene. The photocurrent is ideally suited to measure electronic coherence, as it is a direct result of coherent quantum-path interference, controlled by the delay between two ultrashort two-color laser pulses. The maximum delay for which interference between the population amplitude injected by the first pulse interferes with that generated by the second pulse determines the electronic coherence time. In particular, numerical simulations reveal that the experimental data yields a lower bound on the electronic coherence time, masked by coherent dephasing due to the broadband absorption in graphene. Overall, we expect that our results will significantly advance the understanding of coherent quantum control in solid-state systems ranging from excitation with weak fields to strongly driven systems.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Crystallization of TiO 2 polymorphs from RF-sputtered, amorphous thin-film precursors

Crystalline TiO 2 films of anatase, brookite, and rutile are reproducibly made from amorphous precursors deposited by RF magnetron sputtering, producing large-area, single phase films of uniform thickness. Sputtered amorphous TiO 2 precursor thin films follow the general behavior observed for amorphous precursor thin films generated by pulsed laser deposition, namely, that oxygen deficiency is necessary for the formation of brookite and rutile. We quantify the oxygen deficiency and correlate it with the long wavelength optical absorption. We find that the precursor deposition rate is also a contributing factor to phase selection and that brookite and rutile form from films deposited more rapidly and anatase from films deposited more slowly. Sputtered and pulsed laser deposited amorphous precursor films prepared with similar oxygen deficiency and similar thickness result in the same final state after annealing, but the rate for sputtered precursors is slower.

14 SOLAR ENERGY↗

FEbeam: Cavity and electron emission data conversion, processing, and analysis. A freeware toolkit for rf injectors

FEbeam is an all-in-one field emission data processing interface with the capability to analyze the field emission cathode performance in an rf injector by extracting the field enhancement factor, local field, and effective emission area from the Fowler–Nordheim equations. It also has the capability of processing beam imaging micrographs using its sister software, FEpic. Furthermore, the current version of FEbeam was designed for the Argonne Cathode Test-stand of the Argonne Wakefield Accelerator facility switch yard. With slight modifications, FEbeam could work for many rf field emission injectors. This software is open-source and can be found at GitHub.

43 PARTICLE ACCELERATORS↗

Studying of multi-shell gas-puff Z-pinches using x-ray spectroscopy with spatial resolution

Dynamics and parameters of gas-puff Z-pinch plasmas at stagnation were studied using x-ray spectroscopic diagnostics. In experiments on a 1 MA pulsed power generator, multilayer coaxial loads were made using a triple-nozzle gas-puff valve. High-luminosity spectrographs with spherically bent crystals made it possible to record spectra with high spatial resolution along the pinch axis and to record two-dimensional plasma images in separate spectral lines. Using various combinations of gases in the nozzles and adding small amounts of a gas tracer, the final structure and composition of the compressed plasma were determined. Furthermore, plasma parameters were estimated by modeling the spectra using the PrismSPECT program, but with the limitation that the spectra were time-integrated, so that spectra from different gases and at different positions may have been emitted at different times.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Exploring the parameter space of MagLIF implosions using similarity scaling. III. Rise-time scaling

Magnetized liner inertial fusion (MagLIF) is a z-pinch magneto-inertial-fusion concept studied at the Z Pulsed Power Facility of Sandia National Laboratories. Two important metrics characterizing current delivery to a z-pinch load are the peak current and the current-rise time, which is roughly the time interval to reach the peak current. It is known that, when driving a z-pinch load with a longer current-rise time, the performance of the z-pinch decreases. However, a theory to understand and quantify this effect is still lacking. Here, in this paper, we utilize a framework based on similarity scaling to analytically investigate the variations in the performance of MagLIF loads when varying the current-rise time, or equivalently, the implosion timescale. To maintain similarity between the implosions, we provide scaling prescriptions of experimental input parameters defining a MagLIF load and derive the expected scaling laws for stagnation conditions and for various performance metrics. We compare predictions of the theory to 2D numerical simulations using the radiation, magneto-hydrodynamic code hydra. For several metrics, we find acceptable agreement between the theory and simulations. Our results show that the voltage φload near the MagLIF load follows a weak scaling law φload ∝$t_{φ}^{-0.12}$ with respect to the characteristic timescale t φ of the voltage source, instead of the ideal φload ∝$t_{φ}^{-1}$ scaling. This occurs because the imploding height of the MagLIF load must increase to preserve end losses. As a consequence of the longer imploding liners, the required total laser preheat energy and delivered electric energy increase. Overall, this study helps understand the trade-offs of the MagLIF design space when considering future pulsed-power generators with shorter and longer current-rise times.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Analysis methodology of coherent oscillations in time- and angle-resolved photoemission spectroscopy

Oscillatory signals from coherently excited phonons are regularly observed in ultrafast pump–probe experiments on condensed matter samples. Electron–phonon coupling implies that coherent phonons also modulate the electronic band structure. These oscillations can be probed with energy and momentum resolution using time- and angle-resolved photoemission spectroscopy (trARPES), which reveals the orbital dependence of the electron–phonon coupling for a specific phonon mode. However, a comprehensive analysis remains challenging when multiple coherent phonon modes couple to multiple electronic bands. Complex spectral line shapes due to strong correlations in quantum materials add to this challenge. In this work, we examine how the frequency domain representation of trARPES data facilitates a quantitative analysis of coherent oscillations of the electronic bands. Here, we investigate the frequency domain representation of the photoemission intensity and the first moment of the energy distribution curves. Both quantities provide complementary information and are able to distinguish oscillations of binding energy, linewidth, and intensity. We analyze a representative trARPES dataset of the transition metal dichalcogenide WTe 2 and construct composite spectra, which intuitively illustrate how much each electronic band is affected by a specific phonon mode. We also show how a linearly chirped probe pulse can generate extrinsic artifacts that are distinct from the intrinsic coherent phonon signal.

47 OTHER INSTRUMENTATION↗

Quadrupolar density structures in driven magnetic reconnection experiments with a guide field

Magnetic reconnection is a ubiquitous process in plasma physics, driving rapid and energetic events such as coronal mass ejections. Reconnection between magnetic fields with arbitrary shear can be decomposed into an anti-parallel reconnecting component and a non-reconnecting guide-field component, which is parallel to the reconnecting electric field. This guide field modifies the structure of the reconnection layer and the reconnection rate. We present results from experiments on the MAIZE pulsed-power generator (500 kA peak current, 200 ns rise time), which use two exploding wire arrays, tilted in opposite directions, to embed a guide field in the plasma flows with a relative strength b≡B g /B rec =0, 0.4, or 1. The reconnection layers in these experiments have widths that are less than the ion skin depth, d i =c/ω pi , indicating the importance of the Hall term, which generates a distinctive quadrupolar magnetic field structure along the separatrices of the reconnection layer. Using laser imaging interferometry, we observe quadrupolar structures in the line-integrated electron density, consistent with the interaction of the embedded guide field with the quadrupolar Hall field. Our measurements extend over much larger length scales (40d i ) at higher β (∼1) than previous experiments, providing an insight into the global structure of the reconnection layer.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Generation of few-cycle pulses in media with alternating sign of effective cubic nonlinearity

An original technique is developed for spectral broadening of femtosecond pulses with compensation for the nonlinear spatial phase during the propagation through nonlinear media with effective cubic nonlinearity of different signs. It was shown that in the region of 1.5 μm, the proposed scheme with BBO crystals at the first stage and NaCl at the second stage allows, using chirped mirrors, the formation of few-cycle pulses of about 7 fs duration with a small B-integral. The possibility of focusing of pulses compressed in the proposed scheme with a large Strehl ratio is demonstrated. (paper)

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Mixed stochastic-deterministic time-dependent density functional theory: application to stopping power of warm dense carbon

Warm dense matter (WDM) describes an intermediate phase, between condensed matter and classical plasmas, found in natural and man-made systems. In a laboratory setting, WDM is often created dynamically. It is typically laser or pulse-power generated and can be difficult to characterize experimentally. Measuring the energy loss of high energy ions, caused by a WDM target, is both a promising diagnostic and of fundamental importance to inertial confinement fusion research. However, electron coupling, degeneracy, and quantum effects limit the accuracy of easily calculable kinetic models for stopping power, while high temperatures make the traditional tools of condensed matter, e.g. time-dependent density functional theory (TD-DFT), often intractable. In this study, we have developed a mixed stochastic-deterministic approach to TD-DFT which provides more efficient computation while maintaining the required precision for model discrimination. Recently, this approach showed significant improvement compared to models when compared to experimental energy loss measurements in WDM carbon. Here, we describe this approach and demonstrate its application to warm dense carbon stopping across a range of projectile velocities. We compare direct stopping-power calculation to approaches based on combining homogeneous electron gas response with bound electrons, with parameters extracted from our TD-DFT calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Studies and optimization of hybrid X-pinches

Studies were carried out on the hybrid X-pinch (HXP) configuration for several wire materials using a 40ns risetime, 300-kA pulsed-power generator with the goal of optimizing the HXP X-ray burst parameters for different applications. The gap distance between the conical electrodes of the hybrid X-pinch was varied from 0.5 to 5 mm for Al, Ag, Ti, and Mo using different wire diameters to maintain a consistent mass per unit length from one material to the next. It was found that 0.5 - 1 mm gap spacing was optimal to obtain a single X-ray burst, while the number of X-ray bursts increased with gap spacing for all materials at a rate of 1-2/mm. Time consistency studies of the first X-ray burst were carried out for Ti wire by changing the gap distance and wire diameter while observing the time of occurrence of the X-ray bursts. Here, it was found that a 40μm Ti wire load with a 3mm electrode gap spacing had the highest probability to have the first X-ray burst reproducibly within a 2 ns time window. Time-resolved and time-integrated diagnostics provided information about the source size, time of occurrence, intensity, and the number of the X-ray bursts.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Optical shock-enhanced self-photon acceleration

Photon accelerators can spectrally broaden laser pulses with high efficiency in moving electron density gradients driven in a rapidly ionizing plasma. When driven by a conventional laser pulse, the group velocity walk-off experienced by the accelerated photons and deterioration of the gradient from diffraction and plasma-refraction limit the extent of spectral broadening. In this work, we show that a laser pulse with a shaped space-time and transverse intensity profile overcomes these limitations by creating a guiding density pro le at a tunable velocity. Self-photon acceleration in this profile leads to dramatic spectral broadening and intensity steepening, forming an optical shock that further enhances the rate of spectral broadening. In this new regime, multi-octave spectra extending from 400nm to 60nm wavelengths, which support near-transform limited < 400 as pulses, are generated over < 100 μm of interaction length.

74 ATOMIC AND MOLECULAR PHYSICS↗

State-selective probing of CO 2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy

Nonlinear spectroscopies can disentangle spectra that are congested due to inhomogeneous broadening. Here, in conjunction with theoretical calculations, attosecond extreme ultraviolet (XUV) four-wave-mixing (FWM) spectroscopy is utilized to probe the dynamics of autoionizing inner valence excited Rydberg states of the polyatomic molecule, CO 2 . This tabletop nonlinear technique employs a short attosecond XUV pulse train and two noncollinear, few-cycle near-infrared pulses to generate background-free XUV wave-mixing signals. FWM emission is observed from the n=5-7 states of the Henning sharp ndσ g Rydberg series that converges to the ionic $\widetilde{B}$ 2 Σ$^{+}_{u}$ state. However, these transient emission signals decay with lifetimes of 33 ± 6, 53 ± 2, and 94 ± 2 fs, respectively, which calculations show are consistent with the lifetimes of the short-lived n=6-8 members of the nsσ g character Henning diffuse Rydberg series. The oscillator strengths of transitions between states involved in all possible resonant FWM processes are calculated, verifying that the nonlinear spectra are dominated by pathways described by an initial excitation to the diffuse nsσ g Rydberg series and emission from the sharp ndσ g Rydberg series. The results substantiate not only that attosecond XUV FWM spectroscopy produces rigorous and meaningful measurements of ultrafast dynamics in polyatomic systems, but also that nonlinear spectroscopic techniques are versatile tools to selectively probe dynamics that are otherwise difficult to access.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗