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At least 1,207 records · Page 67

Sixteen multiple-amplifier sensing charge-coupled devices and characterization techniques targeting the next generation of astronomical instruments

We present a candidate sensor for future spectroscopic applications, such as a Stage-5 Spectroscopic Survey Experiment or the Habitable Worlds Observatory. This type of charge-coupled device (CCD) sensor features multiple in-line amplifiers at its output stage allowing multiple measurements of the same charge packet, either in each amplifier or in the different amplifiers. Recently, the operation of an eight-amplifier sensor has been experimentally demonstrated, and we present the operation of a 16-amplifier sensor. This new sensor enables a noise level of ∼1 erms− with a single sample per amplifier. In addition, it is shown that sub-electron noise can be achieved using multiple samples per amplifier. In addition to demonstrating the performance of the 16-amplifier sensor, we aim to create a framework for future analysis and performance optimization of this type of detectors. New models and techniques are presented to characterize specific parameters, which are absent in conventional CCDs and Skipper CCDs: charge transfer between amplifiers and independent and common noise in the amplifiers and their processing.

16 multiple-amplifer sensing CCD (MAS-CCD)↗

Ultra-Light Hybrid Composite Door Design, Manufacturing and Demonstration

New Corporate Average Fuel Economy regulations require improved fuel efficiency of the future vehicle fleet. Weight reduction is key to achieving these targets. Replacing metallic body and chassis components with carbon fiber-reinforced composites offers the most weight reduction potential at up to 70%. Introduction of the BMW i3 and i8 in 2014 required mass production processes to meet 20,000+ units per year. Preforming with High Pressure Resin Transfer Molding has been implemented and meets rate, cost, and performance requirements. We will advance these technologies to develop an ultra-light driver’s side door for the vehicle with production rates of 40,000 units annually per plant in Detroit, Michigan. This project sought to employ a comprehensive systems approach for designing, manufacturing, and demonstrating an ultra-light hybrid composite automotive door. Composite structural components are integrated with other functional systems to reduce part count and full-system weight by a minimum of 42.5%. The approach will be demonstrated on a driver’s- side front door and will consider all fit, functional, safety, and cost requirements. These concepts will be evaluated using structural and crash simulations and linked to a manufacturing feasibility study, resulting in producible designs of an integrated door system. A cost model will evaluate part of the cost for the various designs and will ensure the cost target of less than $5 per pound of weight saved is met. Hybrid composites consisting of carbon, glass, and metal components will be included in our trade-off studies to satisfy these cost and performance goals.

02 PETROLEUM↗

The Transverse and Longitudinal Response Functions in 4He(e,e’) for the Range 0.55 GeV/c lte |q right-arrow| lte 1.0 GeV/c

In electron scattering off a nuclear target, the Coulomb sum is defined as the integration of the longitudinal response function RL over the energy loss of the incident electron in the quasi-elastic nucleon knock-out process. The Coulomb Sum Rule states that at sufficient high three-momentum-transfer |q-right arrow|, the Coulomb sum should equal to the total number of protons in the nucleus: SL -> 1. Previously, precision data existed only up to |q-right arrow| = 600 MeV/c due to the limited beam energy used, and one data point existed for |q-right arrow| = 1.14 GeV/c but with limited precision. During Jefferson Lab experiment E05-110, electron scattering cross sections were measured in the quasi-elastic region on 4He, 12C, 56Fe and 208Pb targets at four scattering angles (15deg., 60deg., 90deg., 120deg.). The longitudinal and transverse response functions RL and RT were extracted in the momentum transfer range 0.55 GeV/c lte |q-right arrow| lte 1.0 GeV/c using the Rosenbluth separation method. The Coulomb sum was formed in the same |q-right arrow| range. The focus of this thesis is the extraction of RL,T from the 4He target data. Preliminary results on RL,T and the Coulomb sum SL for 4He will be presented. The Coulomb sum for 4He is found to be in good agreement with previous data, and still indicate quenching (SL < 1) for the |q-right arrow| region measured by this experiment.

Jin, Kai↗

Saltstone Waste Characterization Analysis - Salt Waste Processing Facility (SWPF) Waste Stream (Q4 CY2020)

The Saltstone Production and Disposal Facility is designed and permitted by the state of South Carolina Department of Health and Environmental Control (SCDHEC) to treat and dispose of low-level radioactive and hazardous liquid waste (salt solution) remaining from the processing of radioactive material at the Savannah River Site (SRS). Low-level waste (LEW) aqueous streams from the Effluent Treatment Project (ETP) and decontaminated solutions from the Tank Closure Cesium Removal Unit (TCCR) and the Salt Waste Processing Facility (SWPF) are stored in Tank 50 until the LEW can be transferred to the Saltstone Facility for treatment and disposal. In the past, decontaminated solution from the Modular Caustic Side Solvent Extraction Unit (MCU) was stored in Tank 50 until the LEW could be transferred to the Saltstone Facility for treatment and disposal. MCU is currently in a suspended operations state. LEW that meets the Waste Acceptance Criteria (WAC) can be transferred, stored, and treated in the Saltstone Production Facility (SPF) for subsequent disposal as saltstone grout in the Saltstone Disposal Facility (SDF). Sampling will be conducted as new waste streams are identified for treatment and disposal at the Saltstone Industrial Wastewater Treatment Facility (IWTF) and Z-Area Industrial Solid Waste Landfill (ISWLF), Facility ID# 025500-1603, General Condition B.9 or every six years in accordance with South Carolina (SC) Regulation 61-107.19 Parti C, “Solid Waste Management: Solid Waste Landfills and Structural Fill - General Requirements.”

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

New Mobility Technology Assessment - Benefits, Risks, and Safety

The age of vehicle automation is upon us. The fundamental perception and control technology is maturing as we speak (and write) with robo-taxis proliferating in select US cities. The news cycle is no longer filled with technological skepticism, but rather societal commentary on our collective response and use of the technology. This maturing of the technology is also accompanied by a renaissance in new types of urban movement technology to more effectively link people with goods, services, and employment, particularly in dense development areas where vehicle congestion (even automated vehicles) prevents high quality mobility. The National Renewable Energy Laboratory, through the DOE Clean Energy to Communities (C2C) program has worked with two jurisdictions to assess the benefits, risks, and safety concerns for a new product offering based on suspended cable technology which is fully automated and proposes an aerial network of self-propelled gondolas. The recognized need, independent of the technology, is to fairly assess the benefits of the proposed transportation system, assess its technical maturity, as well as risks and safety concerns. Using this new technology as an example, a technology represented by Swyft Cities, NREL developed a succession of mini-studies that characterized the technical maturity level, assessed the proposed benefits for Greenville, SC, examined the risks involved in moving forward with an emerging mobility technology, and determined the governing safety protocols and standards that are applicable to the space. These mini-case studies, though centered on Swyft Cities aerial automated gondola technology, are highly transferable to any type of new mobility technology and lays out a repeatable process for assessing new technology within an city or community context.

33 ADVANCED PROPULSION SYSTEMS↗

Miniature sensors with probe insertable into and for obtaining measurements from plants and a variety of other mediums

Apparatus, methods, and systems for transducing measurements from a medium of interest. One non-limiting example is in planta monitoring of plants. In one aspect, a micro- or nano-scale probe body includes one or more microprobes (e.g. microneedles or waveguides) to access desired plant tissue, and one or more microsensors on the probe body. A microcircuit on or in the probe body transduces relevant measurements from the microsensor(s). An output interface allows storage, communication, or transfer of the transduced measurement for further use. Non-limiting examples are processing into estimations of chemical concentrations or the like for biochemical sensing. As such, if used as in planta sensors, they can be minimally invasive and cost effective for both single use and use in sets for plural plants with one central station.

Dong, Liang↗

Development and Performance of RFD Crab Cavity Prototypes for HL-LHC AUP

The US will be contributing to the HL-LHC upgrade at CERN with the fabrication and qualification of RFD crabbing cavities in the framework of the HL-LHC Accelerator Upgrade Project (AUP) managed by Fermilab. AUP received Critical Decision 3 (CD-3) approval by DOE in December 2020 launching the project into the production phase. The electro-magnetic design of the cavity was inherited from the LHC Accelerator Research Program (LARP) but needed to be revised to meet new project requirements and to prevent issues encountered during beam tests performed at CERN in the R&D phase. Two prototype cavities were manufactured in industry and cold tested. Challenges specific to the RFD cavity were the stringent interface tolerances, the pole symmetry, and the higher-order-mode impedance spectrum. Chemical processing and heat treatments were performed initially at FNAL/ANL and are now being transferred to industry for the production phase. HOM dampers are manufactured and validated by JLAB. A summary of cold test results with and without HOM dampers is presented.

43 PARTICLE ACCELERATORS↗

Miniature sensors with probe insertable into and for obtaining measurements from plants and a variety of other mediums

Apparatus, methods, and systems for transducing measurements from medium of interest. One non-limiting example is in planta monitoring of plants. In one aspect, a micro- or nano-scale probe body includes one or more microprobes (e.g. microneedles or waveguides) to access desired plant tissue, and one or more microsensors on the probe body. A microcircuit on or in the probe body transduces relevant measurements from the microsensor(s). An output interface allows storage, communication, or transfer of the transduced measurement for further use. Non-limiting examples are processing into estimations of chemical concentrations or the like for biochemical sensing. As such, if used as in planta sensors, they can be minimally invasive and cost effective for both single use and use in sets for plural plants with one central station.

Dong, Liang↗

Efficient Organic Solar Cell with 16.88% Efficiency Enabled by Refined Acceptor Crystallization and Morphology with Improved Charge Transfer and Transport Properties

Abstract Single‐layered organic solar cells (OSCs) using nonfullerene acceptors have reached 16% efficiency. Such a breakthrough has inspired new sparks for the development of the next generation of OSC materials. In addition to the optimization of electronic structure, it is important to investigate the essential solid‐state structure that guides the high efficiency of bulk heterojunction blends, which provides insight in understanding how to pair an efficient donor–acceptor mixture and refine film morphology. In this study, a thorough analysis is executed to reveal morphology details, and the results demonstrate that Y6 can form a unique 2D packing with a polymer‐like conjugated backbone oriented normal to the substrate, controlled by the processing solvent and thermal annealing conditions. Such morphology provides improved carrier transport and ultrafast hole and electron transfer, leading to improved device performance, and the best optimized device shows a power conversion efficiency of 16.88% (16.4% certified). This work reveals the importance of film morphology and the mechanism by which it affects device performance. A full set of analytical methods and processing conditions are executed to achieve high efficiency solar cells from materials design to device optimization, which will be useful in future OSC technology development.

Zhu, Lei↗

Evaluation of the Potential for Precipitation of Solids during Storage of Non-Aluminum SNF Solutions

Non-aluminum clad spent nuclear fuels (NASNF) stored in the L-Area basin will be dissolved in H-Canyon using the 6.3D electrolytic dissolver. The solutions will be stored in either the hot or warm canyon until the preparation of a sludge batch for the Defense Waste Processing Facility. Spent nuclear fuel solutions could be stored for 1-2 years before transfer to the H-Area Tank Farm depending on the interval between sludge batches. The solution level in the storage tanks will be maintained; therefore, precipitation of solids due to evaporation is not an issue. However, the precipitation of solids from completely dissolved SNF due to solution instabilities has been observed during intermediate storage of solutions generating hydrated oxides.The presence of fissile material in these solids is generally associated with zirconium molybdate, which is known to act as a host lattice for Pu and can carry the actinides upon precipitation. The formation of zirconium molybdate solids which carry fissile material is a potential concern for the storage of NASNF solutions. To address this concern, the Savannah River National Laboratory performed a literature review to identify knowledge gaps which may require experimental work to determine if the formation of solids is a concern during storage of these solutions. Based on the literature review, the precipitation of zirconium molybdate solids from the Campaign 1 NASNF solutions during intermediatestorage is expected. This conclusion is supported by the identification of zirconium molybdate solids found on the H-Canyon 6.1D Dissolver MK-12 insert spacer. The formation of the zirconium molybdate solids is attributed to hydrolysis and radiolytic processes in the nitric acid solution. As the molybdate solids form, U and Pu can substitute for Zr in the crystal lattice resulting in co-precipitation. Generally, the Pu substitutes directly into the crystal lattice during precipitation while the U associated with the molybdate solids more likely absorbs from the solution. The U in the NASNF solutions is present as uranyl nitrate, a 2+ cation which will not substitute as easily into the molybdate crystal lattice for the Zr 4+ ion.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Non-equilibrium plasma generation via nano-second multi-mode laser pulses

The formation and growth of plasma kernels generated via nano-second mode-beating laser pulses is investigated here via a non-equilibrium self-consistent computational model. Chemically reactive Navier–Stokes equations are used to describe the hydrodynamics, and non-equilibrium effects are taken into account with a two-temperature model. Inverse Bremsstrahlung and multiphoton ionization are included self-consistently in the model via a coupled solution of the plasma governing equations and the radiative transfer equation (that describes the laser beam propagation and attenuation). A self-consistent approach (despite carrying additional challenges) minimizes the empiricism and it allows for a more accurate description since it prevents both the utilization of artificial plasma seeds to trigger the breakdown and the implementation of tuning parameters to simulate the laser-energy deposition. The advantages of this approach are confirmed by the good agreement between the numerically predicted and the experimentally measured plasma boundary evolution and absorbed energy. This also holds true for the periodic plasma kernel structures that, as suggested by the experiments and confirmed by the simulations presented here, are connected to the modulating frequency.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Trace Element Control in Master Alloys and Impact of Feedstock Purity on a Ta-containing Steel during Electroslag Remelting

Advanced materials design often leads to new complex compositions that can bring challenges to manufacturing processes. Melt processing of a novel alloy with a tight chemistry range revealed a 25% Ta loss after manufacturing. Vacuum induction melting (VIM) and electroslag remelting (ESR) were performed using industry practices at a laboratory scale and the loss occurred from the VIM electrode to the ESR ingot. Several tools were used for characterization, including combustion analysis, scanning electron microscopy, and electron probe microanalysis for observation of the precipitate and inclusion phases. Additionally, computational modeling of the ESR process was performed to predict macrosegregation and inclusion travel. It was found that a significant amount of Ta2O5 inclusions formed during VIM and were transferred to the slag during ESR. This led to a 95% decrease in density of inclusions explaining to Ta loss. Pathways to better control advanced alloy chemistries during melt processing will be discussed.

Detrois, Martin↗

Smoothed particle hydrodynamics modeling and analysis of oxide reduction process for uranium oxides

A common kinetic feature for oxide reduction chemical/electrochemical processes is oxygen transport via a porous metallic layer, which has been considered as a rate-determining step for reducing uranium oxides to metallic uranium. Accounting this kinetic behavior must involve the resolution of the moving reactive interface between shrinking oxide and expanding metal phases. This study presents a numerical model using smoothed particles hydrodynamics (SPH) to effectively deal with the evolution of the shrinking core reaction interface and oxygen transport via mass transfer of lithium oxide (Li 2 O) species in multiple mass transfer domains. We successfully validated the proposed model against a theoretical derivation for the oxide reduction process handling a shrinking oxide core with molten salt and metal ash medium on a simple planar geometry. Armed with successful validation results, the model examined a realistic reactant geometry to extend the arguments beyond the one-dimensional analyses, allowing the proposed model to apply to general application scenarios with multi-dimensional geometry. Here, this study demonstrated that the proposed model could simulate and evaluate an arbitrary reaction basket design without iterative experimental trials, which is prohibitive for a scaled high-temperature molten salt study in an inert environment. The construct potentially provides not only deep insights on multiphysics behaviors governing the process dynamics but also a robust framework for evaluating and screening candidate basket designs in the most cost-effective manner.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

A molecular dynamics study of collisional heat transfer to nanoclusters in the gas phase

Nanoclusters in the gas phase grow by condensation and coagulation, which heat up nanoclusters, creating thermal non-equilibrium with the surrounding gas. The extent of non-equilibrium for nanoclusters is dependent upon the rate of heating relative to the rate of cooling brought about by nanocluster-gas molecule collisions, hence the latter process plays an important role in nanocluster energy evolution during growth. We apply molecular dynamics simulations to investigate heat transfer between metal nanoclusters and gas molecules relevant to high temperature aerosol systems. In analysis, we first define a thermal reemission coefficient (TRC), which is a correction factor for the portion of energy possessed by reemitted gas molecules after collision. Here, the TRC differs from the thermal accommodation coefficient (TAC), which is a correction factor for the maximum possible energy transfer rate from nanoclusters to gas molecules based on the diffusive collision model. We find the TRC is insensitive to nanocluster size but is affected by the nanocluster to gas temperature ratio and the nanocluster to gas atomic mass ratio. Comparison to the traditionally-defined TAC shows that the TAC is insensitive to temperature, a phenomenon that has been widely indicated in literature but not quantitatively explained. We show how the temperature insensitivity of the TAC arises because of the manner in which TRCs vary with both nanocluster and gas temperature, i.e. the manner in which the reemitted gas molecule energy from a surface varies with the temperature of that surface relative to that of the gas. In addition, while calculations ultimately reveal temperature insensitive TACs and justify their continued use in modeling gas-phase heat transfer, we argue that the TRC is more appropriate to calculate a priori in analyzing simulations; it is physically more realistic to first introduce a correction factor solely for the energy of reemitted gas molecules after a collision (as TRCs) instead of a correction factor applying to both the reemission energy and the initial energy (as TACs), as the latter is exactly calculable and independent of nanocluster properties. In line with prior work, for monoatomic gases we find the TAC decreases as the nanocluster to gas atomic mass increases, approaching 0.08 for gold nanoclusters in helium.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Inkless, dry printing nanographene via in-Situ Coordinated laser ablation and sintering processes

Printing carbon, such as graphene and other carbon structures, for flexible and printed electronics currently relies on either ink-based printing, laser-induced forward transfer (LIFT), or laser-induced graphitization (LIG) to convert carbon-rich precursor materials, such as polymers, to graphene-like carbon structures. Liquid inks contain toxic solvents, surfactants, and stabilizing additives that degrade electrical conductivity and require high-temperature post-processing. On the other hand, LIG is limited by the substrate. Here, this study introduces an additive manufacturing method for dry-printing carbon nanomaterials, ranging from amorphous carbon to crystalline graphene-like structures, on various substrates. The system utilizes laser ablation of a solid graphite target to create pure carbon nanoparticles in situ and on demand. An inert gas carries the nanoparticles onto the substrate, where they can be deposited either as amorphous structures or laser-sintered in real time to form various graphitic structures. The study of laser processing parameters, specifically fluence and pulse repetition frequency, revealed three unique regimes of nanostructure evolution that influence the morphological and electrical properties of these printed structures. Raman spectroscopy confirmed graphitization with a resistivity slightly higher than that of the bulk graphite target. The conductivity/resistivity could be tuned as a function of sintering laser power. Scanning transmission electron microscopy (STEM) revealed that turbostratic nanographene formed with an interlayer spacing of 0.40 nm. Despite ink-based printing methods, such as screen printing, inkjet printing (IJP), and aerosol jet printing (AJP), this eco-friendly and green manufacturing technique could eliminate toxic chemicals, reduce environmental impact, and enable single-step fabrication of carbon-based devices for applications in wearable sensors, energy storage, flexible electronics, and Internet of Things (IoT) devices.

Additive nanomanufacturing↗

Correlation among porosity, mechanical properties, morphology, electronic conductivity and electrochemical kinetics of dry-processed electrodes

Dry processing (DP) has received great interest recently, which poses many advantages over the conventional slurry-based processing. Here, this work investigates the effect of compression on electrode mechanical properties, morphology, electronic conductivity, and electrochemical kinetics. Similar to the slurry-based electrodes, LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC) cathodes with intermediate porosity (i.e., 32%) demonstrate lowest charge transfer resistance, highest electronic conductivity and best rate performance. Fracture of NMC secondary particles is observed in the dry processed NMC cathodes. Reducing electrode porosity results in more fracture in the NMC secondary particles.

25 ENERGY STORAGE↗

Efficient Mesofluidic Separation of Large Particles in nuclear slurries - 20408

Efficient and effective particle separation is essential to cleanup of many nuclear wastes. For example, particle separation may be used to accelerate settle-decant bottlenecks that limit the throughput necessary to achieve the U.S. Department of Energy waste cleanup mission in a timely manner. Particle separation may be used to protect downstream processing equipment from pulses of solids that may be encountered near (within a few feet of) liquid-solid interfaces during waste transfer operations, thereby preventing work stoppages. Effective particle separation may permit efficient sludge washing. These are only a few of the ways in which particle separation is important. Yet, efficient and effective particle separation in nuclear processing environments remains challenging. For example, settle-decant operations permit larger and heavier particles to settle, leaving smaller, lighter particles suspended. However, settle-decant operations are slow, convection currents may resuspend solids, hindered settling of multicomponent slurries remains incompletely understood, and predictive models for settling in graduated cylinders fail to match limited observations of settling in large waste tanks. Additionally, pumping operations can cause turbulent resuspension of particles when the pump intake is close to the settled solids layer. Filtration techniques that use membranes or partially permeable barriers retain larger particles, permitting smaller particles to permeate. However, filters, including dead-end filtration, are prone to clogging and caking, operate at elevated pressures due to minimal void volume, and increase in pressure during operations, which require more control systems. Therefore, the need for high throughput particle separation techniques that operate with modest pressure drops persists. A novel mesofluidic separator presents the opportunity to effectively and efficiently accelerate the waste cleanup mission. The separator separates large particles from process streams across a broad range of particle sizes and has no moving parts or media to replace, regenerate, or clean. This separator design has an unusually large void volume, permitting operation at much higher flow rates (and lower pressures) than traditional filtration (e.g., dead-end filtration). Industrial-scale flow rates have been demonstrated. In performance testing, mesofluidic separators operate at might flow rates (>90 gpm (0.0006 m{sup 3}/s) in piping 3 inches (0.08 m) in diameter; Re>10{sup 5}), with modest pressure drop (∼25 psi (170 KPa) in testing). In complex, aggregating waste simulants, the separator loses <25% of flow projected over months without back pulsing or chemical cleaning. Mesofluidic separation presents infrastructure advantages, reduces risk, and provides mission impact. Infrastructure advantages include implementation within existing transfer systems, plug and play without facility modifications to safety systems, and operation at low pressures. The separator is flexible in location, may be positioned within or outside of waste tanks, and may replace or augment dead-end and cross-flow filters. Mesofluidic separation reduces risk by minimizing waste (no media to replace or regenerate and no cleaning chemicals to handle and dispose) and by minimizing filter change-out consistent with as low as reasonably achievable (ALARA) exposure to workers. The potential mission impact of these separators is substantial. The separator has potential to support, simplify, and accelerate in-farm transfers and waste feed delivery. Furthermore, the separator can free up settling and holding tanks in the Direct Feed Low-Activity Waste (DFLAW) mission by reducing or eliminating post-transfer settling and wait times with the potential to free up 1 Mgal (4000 m{sup 3}) of double-shell tank space. This paper quantitatively compares mesofluidic separation to dead-end filtration, discusses scale-up results, and considers the separator's potential to efficiently and effectively reduce the long-term environmental ability of particulate-rich nuclear wastes. (authors)

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

Illuminating the Photophysics of Oxygen Atom Transfer in Rare Earth Metal-Organic Complexes

Industrial separations of rare earth metals are reliant on selectivity based on ionic radii, which are time, energy, and resource consuming.1 The unique and discontinuous manifold of energy states associated with the f-electron configurations of the rare earth ions2 offer an opportunity to overcome some of these limitations by incorporating light into the separation process. Here, we use transient absorption spectroscopy to understand the differences in mechanism of light-initiated oxygen atom transfer (OAT) in yttrium (Y) and dysprosium (Dy) rare earth complexes. These metal-organic complexes are functionalized with hexfluoroacetyl-acetonate (hfac) and 4-methylmorpholine-N-oxide (NMMO). After light absorption in the presence of triphenyl phosphine (TPP), the NMMO in the Y-NMMO complex is replaced by the TPPO OAT reaction product. Because the Dy f-electron manifold is accessible to the ligand excited states, while there are no accessible states associated with f-electrons for Y, there are significant differences in reactivity. Transient absorption spectroscopy (TAS) was used to monitor changes after 340 nm photoexcitation of Dy/Y-NMMO or the product complex Dy/Y-TPPO. TAS is a pump-probe technique where a white light probe pulse is delayed relative to a visible pump pulse, which photoexcites a sample. Differences between the ground and excited states are monitored over time. With TAS, we access time scales from 100 fs-400 us to determine the photophysics of the complexes of interest. Photoexcitation of Y-NMMO (Fig. 1A) creates a broad photoinduced absorption (PIA) that evolves into a sharp positive feature over 4.2 ps centered at 450 nm. A secondary feature centered at 550 nm grows in with a 200 ps time constant and remains through the 5 ns time window of our experiment. Control experiments for Y-TPPO reveal that the feature at 450 nm is due to internal dynamics of the hfac ligand, while the 550 nm shoulder is due to the presence of the NMMO. Comparing kinetics at 550 nm for Y-NMMO and Dy-NMMO (Fig. 1B) shows that while Y exhibits a distinct growth in the NMMO feature, the Dy decays almost completely within 5 ns. Control experiments with Dy-TPPO prove that the ligand excited states centered on the hfac ligand are deactivated via energy transfer to the Dy manifold within 200 ps. This deactivation leads to significant differences in OAT reactivity between Y and Dy.

CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS↗