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At least 919 records · Page 51

Lone Pairs of Carbogenic Center Enable Thermally Activated Delayed Fluorescence from Carbon to Ligand Charge Transfer Excited States

Carbogenic compounds of the type L→C(0)←L, where L represents various ligands such as phosphines or carbenes, and C(0) denotes zerovalent carbon with two orthogonal lone pairs, are widely utilized in organic and coordination chemistry; however, in-depth photophysical and optical properties remain largely unknown. In the following work, we report detailed luminescent properties of one of the most prominent examples of carbogenic compounds, hexaphenylcarbodiphosphorane (CDP). Combined spectroscopic/TD-DFT studies demonstrate that both lone pairs of CDP participate in the observed visible light absorption and emission, which are associated with carbon lone pairs π*(PPh3) carbon to ligand charge transfer states (CLCTs). The CLCT exhibits a considerably decoupled electron-hole pair, resulting in a small S1-T1 gap and thermally assisted delayed fluorescence (TADF). Moreover, two lone pairs teamed up around C(0) provide numerous close-lying σ- and π-CLCT singlet and triplet states, which allow, for organic TADF emitters, extremely fast rates of exergonic intersystem crossing up to 1.27×109 s-1, competitive with some 3d and 4d metal-based TADF luminophores. These results open fresh directions for innovative design of novel luminescent materials for high-end photonic applications, utilizing lone pairs of carbogenic centers as donors of electron density in the excited states.

Mrózek, Ondřej [University of Southern California]↗

Generation of High-Charge Magnetized Electron Beams Consistent With JLEIC Electron Cooling Requirements

The proposed Jefferson Lab Electron-Ion Collider (JLEIC), currently under design, relies on electron cooling in order to achieve the desired luminosity. This includes an electron beam with >55 Mev, 3.2 nC bunches that cools hadron beams with energies up to 100 GeV. To enhance the cooling, the electron beam must be magnetized with a specific eigen-emittance partition. This paper explores the use of the Fermilab Accelerator Science and Technology (FAST) facility to demonstrate the generation of an electron beam with parameters consistent with those required in the JLEIC high-energy cooler. We demonstrate via simulations the generation of the required electron-beam parameters and perform a preliminary experiment to validate FAST capabilities to produce such beams.

43 PARTICLE ACCELERATORS↗

Influence of Electronic Polarization on the Spectral Density

Accurate spectral densities are necessary for computing realistic exciton dynamics and nonlinear optical spectra of chromophores in condensed-phase environments, including multichromophore pigment–protein systems. However, due to the significant computational cost of computing spectral densities from first principles, requiring many thousands of excited-state calculations, most simulations of realistic systems rely on treating the environment as fixed-point charges. In this work, using a number of representative systems ranging from solvated chromophores to the photoactive yellow protein (PYP), we demonstrate that the quantum mechanical (QM) electronic polarization of the environment is key to obtaining accurate spectral densities and line shapes within the cumulant framework. We show that the QM environment can enhance or depress the coupling of fast chromophore degrees of freedom to the energy gap, altering the electronic–vibrational coupling and the resulting vibronic progressions in the absorption spectrum. In analyzing the physical origin of peaks in the spectral density, we identify vibrational modes that couple the electron and the hole as being particularly sensitive to the QM screening of the environment. For PYP, we reveal the need for careful determination of the appropriate QM region to obtain reliable spectral densities. Our findings suggest that the QM polarization of the environment can be crucial not just for excitation energies but also for electronic–vibrational coupling in complex systems with implications for the correct modeling of linear and nonlinear optical spectroscopy in the condensed phase as well as energy transfer in pigment–protein complexes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Observation of an intermediate state during lithium intercalation of twisted bilayer MoS2

Abstract Lithium intercalation of MoS 2 is generally believed to introduce a phase transition from H phase (semiconducting) to T phase (metallic). However, during the intercalation process, a spatially sharp boundary is usually formed between the fully intercalated T phase MoS 2 and non-intercalated H phase MoS 2 . The intermediate state, i.e ., lightly intercalated H phase MoS 2 without a phase transition, is difficult to investigate by optical-microscope-based spectroscopy due to the narrow size. Here, we report the stabilization of the intermediate state across the whole flake of twisted bilayer MoS 2 . The twisted bilayer system allows the lithium to intercalate from the top surface and enables fast Li-ion diffusion by the reduced interlayer interaction. The E 2g Raman mode of the intermediate state shows a peak splitting behavior. Our simulation results indicate that the intermediate state is stabilized by lithium-induced symmetry breaking of the H phase MoS 2 . Our results provide an insight into the non-uniform intercalation during battery charging and discharging, and also open a new opportunity to modulate the properties of twisted 2D systems with guest species doping in the Moiré structures.

36 MATERIALS SCIENCE↗

Commissioning of the LCLS-II Prototype HOM Detectors with Tesla-Type Cavities at Fast

Experiments at the Fermilab Accelerator Science and Technology* (FAST) facility detected electron beam-induced high order mode (HOM) signals from Tesla superconducting cavities. This paper describes some of the signal detection hardware used in this experiment, as well as measurements of the HOM signal magnitude versus beam trajectory. These measurements were made both with a single bunch and with a train of 50 bunches at bunch charges from 400 pC/b down to 10 pC/b. The detection hardware is designed for use with the Tesla superconducting cavities of LCLS-II at SLAC** and is based on a prototype already in use at Fermilab. The HOM signal passes through a bandpass filter that is centered on several cavity dipole modes and a zero bias Schottky diode detects its magnitude. Direct comparisons were made between the FNAL chassis and the SLAC prototype for identical beam steering conditions. To support measurements with bunch charges as low as 10 pC, the SLAC detector has RF amplification between the bandpass filter and the diode detector. With this hardware, usable HOM signal measurements are obtained with a single bunch of 10 pC in cryomodule cavities as will be needed for LCLS-II.

43 PARTICLE ACCELERATORS↗

A Nonaqueous Redox‐Matched Flow Battery with Charge Storage in Insoluble Polymer Beads**

Abstract We describe the nonaqueous redox‐matched flow battery (RMFB), where charge is stored on redox‐active moieties covalently tethered to non‐circulating, insoluble polymer beads and charge is transferred between the electrodes and the beads via soluble mediators with redox potentials matched to the active moieties on the beads. The RMFB reported herein uses ferrocene and viologen derivatives bound to crosslinked polystyrene beads. Charge storage in the beads leads to a high (approximately 1.0–1.7 M) effective concentration of active material in the reservoirs while preventing crossover of that material. The relatively low concentration of soluble mediators (15 mM) eliminates the need for high‐solubility molecules to create high energy density batteries. Nernstian redox exchange between the beads and redox‐matched mediators was fast relative to the cycle time of the RMFB. This approach is generalizable to many different redox‐active moieties via attachment to the versatile Merrifield resin.

25 ENERGY STORAGE↗

A meshless stochastic method for Poisson–Nernst–Planck equations

A plethora of biological, physical, and chemical phenomena involve transport of charged particles (ions). Its continuum-scale description relies on the Poisson–Nernst–Planck (PNP) system, which encapsulates the conservation of mass and charge. The numerical solution of these coupled partial differential equations is challenging and suffers from both the curse of dimensionality and difficulty in efficiently parallelizing. We present a novel particle-based framework to solve the full PNP system by simulating a drift–diffusion process with time- and space-varying drift. We leverage Green’s functions, kernel-independent fast multipole methods, and kernel density estimation to solve the PNP system in a meshless manner, capable of handling discontinuous initial states. The method is embarrassingly parallel, and the computational cost scales linearly with the number of particles and dimension. We use a series of numerical experiments to demonstrate both the method’s convergence with respect to the number of particles and computational cost vis-à-vis a traditional partial differential equation solver.

Chemistry↗

Engineering Functionalized 2D Metal-Organic Frameworks Nanosheets with Fast Li + Conduction for Advanced Solid Li Batteries

Solid-state batteries can ensure high energy density and safety in lithium metal batteries, while polymer electrolytes are plagued by slow ion kinetics and low selective transport of Li + . Metal-organic frameworks (MOFs) are proposed as emerging fillers for solid-state poly(ethylene oxide)(PEO) electrolytes, however, developing functionalized MOFs and understanding their roles on ion transfer has proven challenging. Herein, combining computational and experimental results, the functional group regulation in MOFs can effectively change surficial charge distribution and limit anion movement is revealed, providing a potential solution to these issues. Specifically, functionalized 2D MOF sheets are designed through molecular engineering to construct high-performance composite electrolytes, where the electron-donating effect of substituents in 2D-MOFs effectively limits the movement of ClO 4 - and promotes mechanical properties and ion migration numbers (0.36 up to 0.64) of PEO. As a result, Li/Li cells with composite electrolyte exhibit superior cyclability for 1000 h at a current density of 0.2 mA cm -2 . Meanwhile, the solid LiFePO 4 /Li battery delivers highly reversible capacities of 148.8 mAh g -1 after 200 cycles. In conclusion, these findings highlight a new approach for anion confinement through the use of functional group electronic effects, leading to enhanced ionic conductivity, and a feasible direction for high-performance solid-state batteries.

25 ENERGY STORAGE↗

Design and additive manufacturing of optimized electrodes for energy storage applications

Supercapacitors exhibit fast charging/discharging ability and have attracted considerable attention within the automotive, aerospace, and telecommunication industries. Porous carbons, prized for their high electrical conductivity and high surface area, have been attractive candidates for supercapacitor electrodes. Moving to thick electrodes is one strategy to further increase energy density due to a higher volume fraction of active material. However, thick electrodes suffer from sluggish charged species transport, which is why thin electrodes are currently favored. In this work, we investigate the use of computational optimization and additive manufacturing to design and fabricate thick porous electrodes with improved performance. Electrode performance was maximized by designing their morphologies via topology optimization and printing by projection micro stereolithography (PμSL) using commercial resin (PR48). The PR48 resin was then pyrolyzed (PR48-P) to create the final conductive electrode. The optimized PR48-P electrodes exhibited 99% improvement in capacitance compared to control electrodes printed with cubic lattice morphologies. To further improve performance, we formulated a resin combining graphene oxide (GO) and trimethylolpropane triacrylate (TMPTA). Electrodes printed with 3 wt% GO in TMPTA exhibited improved capacitance retention after pyrolysis compared to the PR48-P electrodes. Finally, this work demonstrates the benefits of using topology optimization to design electrodes and material development to improve functional properties of 3D printable electrodes.

25 ENERGY STORAGE↗

Enabling the Acquisition of Electron Beam-Induced Current (EBIC) Images in Conventional SEM and STEM Instruments

Electron beam-induced current (EBIC) imaging is a well-established scanning electron microscope (SEM) technique used to analyze the behavior of microelectronic devices including solar cells. Recently, the application of EBIC imaging in an aberration-corrected scanning transmission electron microscope (STEM) has been demonstrated and offers great potential for the in situ study of electronic materials, correlating charge transport properties to atomic structural and elemental information. Here, this work presents two ways to implement EBIC imaging in conventional SEM and STEM systems: one relying on the instrument's inherent scanning and imaging electronics and the other involving third-party systems usually available in electron microscopes. The implementation of lock-in EBIC in systems equipped with a fast beam blanker is also described. In addition, this work shows and discusses the different mechanisms at play in EBIC imaging and their dependence on beam energy, sample impedance, and electrical measurement configuration, providing researchers with the basic information needed to apply the technique to their research.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Characterization of carrier behavior in photonically excited 6H silicon carbide exhibiting fast, high voltage, bulk transconductance properties

Abstract Unabated, worldwide trends in CO 2 production project growth to > 43-BMT per year over the next two decades. Efficient power electronics are crucial to fully realizing the CO 2 mitigating benefits of a worldwide smart grid (~ 18% reduction for the United States alone). Even state-of-the-art SiC high voltage junction devices are inefficient because of slow transition times (~ 0.5-μs) and limited switching rates at high voltage (~ 20-kHz at ≥ 15-kV) resulting from the intrinsically limited charge carrier drift speed (< 2 × 10 7 -cm-s −1 ). Slow transition times and limited switch rates waste energy through transition loss and hysteresis loss in external magnetic components. Bulk conduction devices, where carriers are generated and controlled nearly simultaneously throughout the device volume, minimize this loss. Such devices are possible using below bandgap excitation of semi-insulating (SI) SiC single crystals. We explored carrier dynamics with a 75-fs single wavelength pump/supercontinuum probe and a modified transient spectroscopy technique and also demonstrated a new class of efficient, high-speed, high-gain, bi-directional, optically-controlled transistor-like power device. At a performance level six times that of existing devices, for the first time we demonstrated prototype operation at multi-10s of kW and 20-kV, 125-kHz in a bulk conduction transistor-like device using direct photon-carrier excitation with below bandgap light.

36 MATERIALS SCIENCE↗

Modular Design of Receiver Side Power Electronics for 200 kW High Power Dynamic Wireless Charging System

Dynamic wireless power transfer (DWPT) can provide energy to EVs in motion and extend the drive range. By upscaling the charging power to 200 kW (High Power DWPT), the percentage of electrified roadway reduces and the solution becomes cost-effective. However, coil coupling-coefficient variation during vehicle movement fluctuates the transferred power which is unfavorable for vehicle battery. Secondary regulation design can smooth the power but the converter design becomes very challenging due to requirement in high power, high efficiency, fast control, as well as high power density since the unit will be onboard. This paper provides the modular design approach of a 200 kW secondary side unit to achieve high performance and scalability. The DC/DC converter using SiC devices demonstrated 98.3% efficiency.

Xue, Lincoln↗

The ETROC2 as the Final Version for CMS Endcap Timing Layer (ETL) Upgrade

The ETROC (Endcap Timing Readout Chip) is being developed for the LGAD-based CMS Endcap Timing Layer (ETL) at HL-LHC. The ETL on each side of the interaction region will be instrumented with a two-disk system of MIP-sensitive LGAD (Low Gain Avalanche Diodes) silicon devices, read out by ETROCs for precision timing measurement with down to ~30 ps timing resolution per track. The ETROC is designed to handle a 16 x 16 pixel cell matrix, with each pixel being 1.3 mm x 1.3 mm to match the LGAD sensor pixel size. The front-end design for preamplifier and discriminator has been specifically optimized for the reduced LGAD signals, with enough flexibilities to meet the ETL specific needs for time resolution, power budget and radiation profile. The ETROC chip is implemented in a commercial 65nm CMOS process. Each channel consists of a preamplifier, a discriminator, a TDC used for TOA (Time Of Arrival) and TOT (Time Over Threshold) measurements, and a memory for data storage and readout. An in-pixel auto threshold calibration is included, along with a self-testing pattern generator. The TOT is used for time-walk correction of the TOA measurement. The detailed hit information (TOA and TOT) from each cell will be read out from a local circular buffer after each Level-1 Accept (about 1 MHz). In addition, a charge injection circuit is implemented to allow for testing and calibration. For more detailed monitoring of the signal pulses, waveform sampling circuits are included for one pixel. The clock distribution is based on a 16x16 H-tree design with a shielding structure to alleviate potential interference. The global peripheral circuits include a PLL, a phase shifter, an I2C slave controller, a fast control block, a global readout, and a data driver along with an efuse and temperature sensor. The ETROC builds event data frames for each L1A selected event and is also capable of providing L1 trigger information for user-defined delayed hits. The main design challenge is how to extract precision timing information from the small LGAD signals in the presence of high irradiation fluence, while keeping the power consumption and digital activity low. The ETL design goal for the time resolution of 50 ps per hit is required to achieve a 35 ps arrival time measurement for a MIP particle, which has its track registered in two ETL disk layers. The LGAD contribution is known to be about 30 ps, this means that the jitter from the ETROC has to be kept below 40 ps. The ETROC2 is the first full size full functionality prototype design fully compatible with the final chip specifications for CMS ETL and now becomes the final version. The ETROC2 chips have been extensively tested. We will present here new testing results including the bump bonding yield improvement study, the time walk correction (TWC) generality study with one pixel TWC applying to all pixels, the final SEU testing using both heavy ion and proton beam, more beam test studies including different sensors, and readiness for the ETROC2 production for CMS ETL upgrade.

Liu, Tiehui [Fermilab] (ORCID:0009000765225605)↗

Measurement of Charged-Pion Production in Deep-Inelastic Scattering off Nuclei with the CLAS Detector

Background: Energetic quarks in nuclear deep-inelastic scattering propagate through the nuclear medium. Processes that are believed to occur inside nuclei include quark energy loss through medium-stimulated gluon bremsstrahlung and intranuclear interactions of forming hadrons. More data are required to gain a more complete understanding of these effects. Purpose: To test the theoretical models of parton transport and hadron formation, we compared their predictions for the nuclear and kinematic dependence of pion production in nuclei. Methods: We have measured charged-pion production in semi-inclusive deep-inelastic scattering off D, C, Fe, and Pb using the CLAS detector and the CEBAF 5.014-GeV electron beam. We report results on the nuclear-to-deuterium multiplicity ratio for π + and π - as a function of energy transfer, four-momentum transfer, and pion energy fraction or transverse momentum—the first three-dimensional study of its kind. Results: The π + multiplicity ratio is found to depend strongly on the pion fractional energy z and reaches minimum values of 0.67 ± 0.03, 0.43 ± 0.02, and 0.27 ± 0.01 for the C, Fe, and Pb targets, respectively. The z dependencies of the multiplicity ratios for π + and π - are equal within uncertainties for C and Fe targets but show differences at the level of 10% for the Pb-target data. The results are qualitatively described by the GIBUU transport model, as well as with a model based on hadron absorption, but are in tension with calculations based on nuclear fragmentation functions. Conclusions: These precise results will strongly constrain the kinematic and flavor dependence of nuclear effects in hadron production, probing an unexplored kinematic region. They will help to reveal how the nucleus reacts to a fast quark, thereby shedding light on its color structure and transport properties and on the mechanisms of the hadronization process.

Moran, S.↗

A Particle-in-Cell Method for Plasmas with a Generalized Momentum Formulation, Part I: Model Formulation

Here, this paper formulates a new particle-in-cell method for the Vlasov–Maxwell system. Under the Lorenz gauge condition, Maxwell’s equations for the electromagnetic fields can be written as a collection of scalar and vector wave equations. The use of potentials for the fields motivates the adoption of a Hamiltonian formulation for particles that employs the generalized (conjugate) momentum. A notable advantage offered by the Hamiltonian formulation is the elimination of time derivatives in the Lorenz gauge formulation that are required by the standard Newton–Lorentz treatment of the particles. This allows the fields to retain the full time-accuracy guaranteed by the field solver. The resulting updates for particles require only knowledge of the fields and their spatial derivatives. An analytical method for constructing these spatial derivatives is presented that exploits the underlying integral solution used in the field solver for the wave equations. Moreover, these derivatives are demonstrated to converge at the same rate as the fields in both time and space. The Method of Lines Transpose field solver we consider in this work is globally first-order accurate in time and high-order accurate in space (e.g., fourth- and fifth-order) and belongs to a larger class of methods which are unconditionally stable, can address geometry, and leverage $\mathcal {O}(N)$ fast summation methods for efficiency. We demonstrate the method on several well-established benchmark problems on bounded domains, including a plasma sheath as well as a relativistic particle beam. The efficacy of the proposed formulation is established by comparing with a second-order accurate finite-difference time-domain method that employs a leapfrog time advance for particles and a charge conserving map suitable for bounded domains. The new method shows mesh-independent numerical heating properties even in cases where the plasma Debye length is smaller than the grid spacing. This is an important feature of the new method for problems defined on bounded domains, because it permits the use of coarser grids in space in the representation of the fields. Such a capability has significant implications for the simulation of plasmas in bounded domains with complex geometry, where the ratio between the largest and smallest cells can vary significantly. The use of high-order spatial approximations in the new method also means that fewer grid points are required in order to achieve a fixed accuracy. Our results also suggest that the new method can be used with fewer simulation particles per cell compared to the benchmark explicit method, which permits further computational savings.

97 MATHEMATICS AND COMPUTING↗

Controlled Hysteresis of Conductance in Molecular Tunneling Junctions

The problem this paper addresses is the origin of the hysteretic behavior in two-terminal molecular junctions made from an EGaIn electrode and self-assembled monolayers of alkanethiolates terminated in chelates (transition metal dichlorides complexed with 2,2'-bipyridine; BIPY-MCl 2 ). The hysteresis of conductance displayed by these BIPY-MCl 2 junctions changes in magnitude depending on the identity of the metal ion (M) and the window of the applied voltage across the junction. The hysteretic behavior of conductance in these junctions appears only in an incoherent (Fowler–Nordheim) tunneling regime. When the complexed metal ion is Mn(II), Fe(II), Co(II), or Ni(II), both incoherent tunneling and hysteresis are observed for a voltage range between +1.0 V and –1.0 V. When the metal ion is Cr(II) or Cu(II), however, only resonant (one-step) tunneling is observed, and the junctions exhibit no hysteresis and do not enter the incoherent tunneling regime. Using this correlation, the conductance characteristics of BIPY-MCl 2 junctions can be controlled. Furthermore, this voltage-induced change of conductance demonstrates a simple, fast, and reversible way (i.e., by changing the applied voltage) to modulate conductance in molecular tunneling junctions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

99 TcO 4 - removal from legacy defense nuclear waste by an alkaline-stable 2D cationic metal organic framework

Removal of 99 TcO 4 - from legacy defense nuclear tank waste at Savannah River Site is highly desirable for the purpose of nuclear safety and environmental protection, but currently not achievable given the extreme conditions including high alkalinity, high ionic strength, and strong radiation field. Herein, we present a potential solution to this long-term issue by developing a two-dimensional cationic metal organic framework SCU-103, showing ultrahigh stability in alkaline aqueous media and great resistance to both β and γ radiation. More importantly, it is very effective for 99 TcO 4 - separation from aqueous media as demonstrated by fast exchange kinetics, high sorption capacity, and superior selectivity, leading to the successful removal of 99 TcO 4 - from actual Savannah River Site high level tank waste for the first time, to the best of our knowledge. In addition, the uptake mechanism is comprehensively elucidated by molecular dynamics simulation and density functional theory calculation, showing a unique chemical recognition of anions with low charge density.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗

Ion density waves driving the formation of filamentary dust structures

The PlasmaKristall-4 (PK-4) experiment on the International Space Station allows for the study of the 3-dimensional interaction between plasma and dust particles. Previous simulations of the PK-4 environment have discovered fast moving ionization waves in the dc discharge. These ionization waves vary the plasma parameters by up to an order of magnitude, which may affect the mechanisms responsible for the self-organization of chains seen in the PK-4 experiment. Here, we adapt a molecular dynamics simulation to employ temporally varying plasma conditions in order to investigate the effect on the dust charging and electrostatic potential. In order to describe the differences between the average of the plasma conditions and the time-varying plasma condition, we present a model to reproduce the interaction that takes into account the negative potential from the dust grain and the positive potential from the ion wake.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗