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CTF Theory Manual (V.4.2)

Coolant-Boiling in Rod Arrays—Two Fluids (COBRA-TF) is a thermal/hydraulic (T/H) simulation code designed for light water reactor (LWR) vessel analysis. It uses a two-fluid, three-field (i.e. fluid film, fluid drops, and vapor) modeling approach. Both sub-channel and 3D Cartesian forms of 9 conservation equations are available for LWR modeling. The code was originally developed by Pacific Northwest Laboratory in 1980 and had been used and modified by several institutions over the last few decades. COBRA-TF also found use at the Pennsylvania State University (PSU) by the Reactor Dynamics and Fuel Modeling Group (RDFMG) and has been improved, updated, and subsequently re-branded as CTF. As part of the improvement process, it was necessary to generate sufficient documentation for the open-source code which had lacked such material upon being adopted by RDFMG. This document serves mainly as a theory manual for CTF, detailing the many two-phase heat transfer, drag, and important accident scenario models contained in the code as well as the numerical solution process utilized. Coding of the models is also discussed, all with consideration for updates that have been made when transitioning from COBRA-TF to CTF. Further documentation outside of this manual is also available at RDFMG which focus on code input deck generation and source code global variable and module listings

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Semi-Annual Report for Horizontal Compact High Temperature Gas Reactor (HC-HTGR) Development during Performance Period October 2022-March 2023

Horizontal Compact High Temperature Gas Reactor (HC-HTGR) is being designed by a multi-disciplinary team of nuclear, mechanical, and structural engineers under the support of a DOE-NE Advanced Reactor Demonstration Program’s Advanced Reactor Concepts-20 (ARC-20) award. The objective of this ARC-20 project is to deliver a conceptual design for the proposed HC-HTGR in 3 years and support its commercialization as a safe, low-cost HTGR. Argonne National Laboratory (Argonne) is responsible for the design and analysis of the reactor cavity cooling system (RCCS) as a safety system for passive decay heat removal of the reactor concept. Additionally, Argonne is providing analysis of the primary heat transport system to ensure temperatures in the reactor systems, structures and components with significant safety margins during normal operation and design basis accident scenarios. This third semi-annual report summarized the progress made at Argonne on the two tasks during the first half of FY23. As a part of the RCCS design task, a design process for the water panel and the system configuration was performed to improve the thermal performance of the RCCS. The updated water panel design had achieved enhanced thermal performance with 0.96 MWth capability with major design updates made in structural interfaces with the RPV and initial configuration of the water tanks. The loop configuration of the RCCS has been proposed to have two independently working loops for system redundancy. A water panel material study was performed focusing on the use of carbon steel in water systems. Additional modeling strategies of primary system thermal fluids analyses were developed to meet modeling needs that are not well suited for the 1D-3D assembly level approach. The first of these is a reduced order assembly model, in which fuel centered unit cells are used to represent a fuel assembly. The 2D approach used in this model is much more computationally efficient, making this model useful for full core transient scenarios where fuel to coolant heat transfer is still the dominant flow path. The next model is the 3D core conduction model to be used to analyze decay heat removal in loss of primary system flow scenarios. Because these scenarios require a large domain to be modeled, a homogenized core model is being pursued to reduce the required computational costs. To accurately model decay heat scenarios it is necessary to couple a RCCS model to the 3D core conduction model. A simplified case is presented to demonstrate how the coupling methodology will be applied to the full core 3D conduction model.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

CTF Theory Manual: Version 4.3

Coolant-Boiling in Rod Arrays—Two Fluids (COBRA-TF) is a thermal/hydraulic (T/H) simulation code designed for light water reactor (LWR) vessel analysis. It uses a two-fluid, three-field (i.e., fluid film, fluid drops, and vapor) modeling approach. Both subchannel and three-dimensional Cartesian forms of its governing equations are available for the solution. The code was originally developed by Pacific Northwest Laboratory in 1980, and had been used and modified by several institutions over the last few decades. COBRA-TF also found use at the Pennsylvania State University (PSU) by the Reactor Dynamics and Fuel Modeling Group (RDFMG) and has been improved, updated, and subsequently rebranded as CTF. CTF was later adopted in the early 2010s by Oak Ridge National Laboratory (ORNL) for use in the Consortium for Advanced Simulation of Light Water Reactors (CASL) program, which led to a significant advancement of the code software quality, modeling accuracy, testing systems, and capabilities for improved support of modeling of common LWR nominal and transient behavior. As part of the improvement process, it was necessary to generate sufficient documentation for the public domain code which had lacked such material upon being adopted by RDFMG. This document serves as a theory manual for CTF, detailing the many two-phase heat transfer, drag, and important accident scenario models contained in the code, as well as the numerical solution process utilized. Additional documents available in the CTF documentation suite include the user manual and verification and validation manual.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

CTF Theory Manual: Version 4.4

Coolant-Boiling in Rod Arrays – Two Fluids (COBRA-TF) is a thermal/hydraulic (T/H) simulation code designed for light-water reactor (LWR) vessel analysis. It uses a two-fluid, three-field (i.e., fluid film, fluid drops, and vapor) modeling approach. Both subchannel and 3D Cartesian forms of its governing equations are available for the solution. The code was originally developed by Pacific Northwest Laboratory in 1980 and has been used and modified by several institutions over the last few decades. COBRA-TF also found use at the Pennsylvania State University (PSU) by the Reactor Dynamics and Fuel Modeling Group (RDFMG) and has been improved, updated, and subsequently rebranded as CTF. CTF was later adopted in the early 2010s by Oak Ridge National Laboratory (ORNL) for use in the Consortium for Advanced Simulation of Light Water Reactors (CASL) program, which led to a significant advancement of the code’s software quality, modeling accuracy, testing systems, and capabilities for improved support in modeling common LWR nominal and transient behavior. As part of the improvement process, it was necessary to generate sufficient documentation for the public domain code which had lacked such material upon being adopted by RDFMG. This document serves as a theory manual for CTF, detailing the many two-phase heat transfer, drag, and important accident scenario models contained in the code, as well as the numerical solution process utilized. Additional documents available in the CTF documentation suite include the user manual and the verification and validation manual.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

MOSCATO Development and Integration in Fiscal Year 2025: Implementation of Multiphase, Multiphysics Modeling Capabilities for Molten Salt Systems

MOSCATO (Molten Salt Chemistry and Transport) is a multiphysics code that provides high-fidelity, coupled simulations of fluid flow, heat transfer, mass transfer, chemistry, electrochemical phenomena, and alloy corrosion for molten salt systems. In FY25, significant developments were made to the code package, enhancing its capabilities for modeling all relevant phenomena within operating moltens salt reactors (MSRs). The developments and activities in FY25 included: 1. Implementation of Level-Set methods to enable modeling of single-bubble behavior in molten salts. In FY25, the Level-Set two-phase flow modeling implementation was improved to simulate single bubble behavior with molten salt media. The large density and viscosity ratios between typical gases and molten salt liquids present challenges for these types of numerical solvers. With enhancements to the pressure projection method, MOSCATO’s Level-Set solver was able to be successfully validated to experiments related to helium bubble rise in stagnant molten salt. The simulated bubble rising velocity showed reasonable good agreement with experimental measurements. The bubble shape and dynamics were also visually compared with experimental snapshots, demonstrating a good qualitative match. 2. Generation of mass transfer correlations for multiphase flow systems. To enable calculations of the tritium transport across the interface between gas bubbles and salt, we modeled high- Schmidt-number mass transfer around a sphere across a broad range of Reynolds numbers. The mesh near the sphere surface was highly refined to resolve steep concentration gradients caused by the low diffusion coefficient. Literature-based mass transfer correlations were compared with the numerical results, and modifications were proposed to improve agreement, particularly at higher Schmidt numbers. These mass transfer correlations were subsequently provided to other national laboratories to help enable high quality mass transfer simulations using lower-order solvers under development within the NEAMS program. 3. Preliminary implementation of a bubbly flow solver. To model bubbly flow in molten salt, we implemented a bubbly flow solver for void fractions less than 5%. To do so, an algebraic relative velocity model that assumes small bubbles with rapid momentum equilibration was added to MOSCATO to compute bubble velocities. Preliminary comparisons with experimental data showed reasonable agreement, and further improvements are underway. 4. Generation of mass transfer correlations for MSRE subchannel The Molten-Salt Reactor Experiment (MSRE) was a landmark historical project that demonstrated the feasibility of molten-salt reactor technology. The MSRE campaign also generated a significant body of experimental data and reports that continue to support molten-salt–related research. In this report, the MSRE core subchannel was used as the reference geometry for a mass transfer study performed with MOSCATO. The geometry and computational mesh were adapted from a previous study, providing adequate resolution for the relatively low Reynolds number in this case. Additional mesh refinement was applied to reach higher Schmidt numbers, enabling the derivation of a reliable mass-transfer correlation for the present scenario. 5. Simulations of oxygen ingressions into molten salt. In the previous fiscal year, we initiated a study to simulate oxygen ingression in stagnant salt. As oxygen enters the salt through its surface, it reacts with Ce 3+ to form solid CeO 2 and other reaction products. To more fully capture the complex diffusion-convection-reaction mechanisms, capabilities for modeling natural convection in the salt vessel were added. These were needed as the flow of the ingressed gas induced flow in the salt caused by surface shear and non-isothermal effects. With these updated physics in place, we were able to successfully reproduce the experimental results for the rate of change of CeCl 3 concentrations versus time. 6. Flow corrosion model validation. In FY24, MOSCATO’s corrosion model was validated against static corrosion experiments. In FY25, this work was extended to a flow corrosion experiment, where FLiNaK salt was driven by natural convection, with initial salt impurities to initiate corrosion. Despite uncertainties in parameters such as elemental diffusion coefficients in the alloy and unknown H + concentrations, the simulations achieved good agreement with experimental results, especially in predicting sample mass losses.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

The ESA mission to Comet Halley

The Europeon Space Agency's approximately Giotto mission plans for a launch in July 1985 with a Halley encounter in mid-March 1986 4 weeks after the comet's perihelion passage. Giotto carries 10 scientific experiments, a camera, neutral, ion and dust mass spectrometers, a dust impact detector system, various plasma analyzers, a magnetometer and an optical probe. The instruments are described, the principles on which they are based are described, and the experiment key performance data are summarized. The launch constraints the helicentric transfer trajectory, and the encounter scenario are analyzed. The Giotto spacecraft major design criteria, spacecraft subsystem and the ground system are described. The problem of hypervelocity dust particle impacts in the innermost part of the coma, the problem of spacecraft survival, and the adverse effects of impact-generated plasma aroung the spacecraft are considered.

Reinhard, R.↗

The faint young sun-climate paradox - Volcanic influences

It has been suggested that the early earth may have frozen over as a result of a fainter early sun (see Ulrich, 1975). If this had happened, climate models suggest the earth would have remained frozen through the present epoch and into the distant future. We suggest that volcanic influences could allow a passage from the frozen branch into the unfrozen branch of climate models should conditions on earth be suitable for the latter climate change. A broad equatorial belt of volcanic ash is one scenario which would allow a transfer from the frozen earth state into the unfrozen one.

Schatten, K. H.↗

The faint young sun-climate paradox - Crustal influences

The various mechanisms which have been proposed to compensate for the climatic effects of a 30 percent increase in the solar constant during the past 4.5 billion years are examined. Mechanisms besides the greenhouse effect could have provided significant compensation during the second half of this period. It is proposed that the development of continents during the past 2.5 billion years caused a secular evolution of the atmosphere-ocean heat transport system. As a result, past climates were less susceptible to complete freeze-over. The lower albedo of water would be another factor in this effect insofar as the early earth had smaller land masses. A complete or nearly complete freeze-over may have occurred as past glaciations were widespread. Climate models then suggest that the earth would have remained frozen through the present epoch and into a distant future. It is suggested that volcanic influences could allow a passage from the frozen branch onto the unfrozen branch of climate models should conditions on earth be suitable for that climate change. A broad equatorial belt of volcanic ash is one scenario which would allow a transfer from the frozen earth state into the unfrozen one.

Schatten, K. H.↗

Servicing operations for the SIRTF Observatory at the Space Station

This paper describes the servicing requirements, plans, and proposed Space Station-based servicing operations for the Space Infrared Telescope Facility (SIRTF) Observatory. SIRTF is a cryogenically-cooled, long-life, one meter class space telescope which will be operated by NASA as a free-flying observatory for infrared astronomy, in the mid-1990's. To achieve its 5-year lifetime requirement (10 year goal), SIRTF must be replenished periodically with cryogenic helium and have its life-limited modular subsystems replaced; capability for contingency repair of warm components will also be provided in the Observatory design. A general description of the SIRTF Observatory is given, including options for the support systems (spacecraft). The overall servicing philosophy and plans are addressed with scheduling and needed support elements described. A proposed Space Station-based servicing scenario is described, including orbital transfer, servicing and checkout operations. A detailed description and timeline for liquid helium replenishment operations is provided, including a conceptual design and technology development program for the cryogenic helium transfer dewar (tanker). Finally, a preliminary SIRTF spares/logistics philosophy is outlined, including tradeoffs to be considered.

Wiltsee, Christopher B.↗

Autonomous integrated GPS/INS navigation experiment for OMV. Phase 1: Feasibility study

The phase 1 research focused on the experiment definition. A tightly integrated Global Positioning System/Inertial Navigation System (GPS/INS) navigation filter design was analyzed and was shown, via detailed computer simulation, to provide precise position, velocity, and attitude (alignment) data to support navigation and attitude control requirements of future NASA missions. The application of the integrated filter was also shown to provide the opportunity to calibrate inertial instrument errors which is particularly useful in reducing INS error growth during times of GPS outages. While the Orbital Maneuvering Vehicle (OMV) provides a good target platform for demonstration and for possible flight implementation to provide improved capability, a successful proof-of-concept ground demonstration can be obtained using any simulated mission scenario data, such as Space Transfer Vehicle, Shuttle-C, Space Station.

Upadhyay, Triveni N.↗

Handbook for Using IP Protocols for Space Missions

This presentation will provide a summary of a handbook developed at GSFC last year that contains concepts and guidelines for using Internet protocols for space missions. It will include topics on: Lessons learned from current Space IP mission. General architectural issues related to use of IP in space. Operational scenarios for common space data transfer applications. Security issues. A general review of protocols applicable for use with IP in space. The presentation will also pose questions on what sort of information would be useful in future versions of the document.

Hogie, Keith↗

Fluorescence Correction Vegetation Index (FCVI): A physically based reflectance index to separate physiological and non-physiological information in far-red sun-induced chlorophyll fluorescence

Sun-induced chlorophyll fluorescence (SIF) has been used to track vegetation photosynthetic activity for improving estimation of gross primary productivity (GPP) and detecting plant stress. There are both physical and physiological controls of SIF measured at the surface and retrieved from remote sensing including satellite observations. In order to accurately use SIF for monitoring of plant physiology, the effects of physically-based radiation processes related to leaf and canopy structure, notably photosynthetically active radiation (PAR) absorption and SIF scattering and re-absorption, must be characterized. In this study, we investigate both PAR absorption and SIF scattering processes and find that although it is difficult to quantify their effects individually by using just reflectance, the combined effects of the two processes can be well approximated by a reflectance index. This index, referred to as FCVI (Fluorescence Correction Vegetation Index), is defined as the difference between near-infrared (NIR) and broad-band visible (VIS, 400–700 nm) reflectance acquired under identical sun-canopy-observer geometry of the SIF measurements. The development of the index was based on the physical connection between reflectance and far-red SIF, which was revealed by using the spectral invariant theory. The utility of FCVI to correct far-red SIF for PAR absorption and scattering effects, thus improving the link to photosynthesis, was tested with data from: (i) a field experiment for a growing season; and (ii) a numerical experiment which included a number of scenarios generated by a radiative transfer model. For both the observations and simulations, the FCVI provided a promising estimate of the impact of the physically-based radiation processes on far-red SIF of moderately dense canopies (i.e., FCVI ≥ 0.18). Normalizing the TOC far-red SIF by both the incident PAR (iPAR) and the FCVI provided a good estimate of the far-red fluorescence emission efficiency of the canopies examined. This approach enhances our ability to generalize retrievals for vegetation processes as they change through natural growth phases and seasons. Taken together, far-red SIF and FCVI may enable the assessment of the light partitioning of vegetation canopies, an essential step to facilitate the use of far-red SIF for tracking physiological processes.

Peiqi Yang↗

Leveraging Observing System Simulation Experiments for Satellite Instrument Design: Advancements and Challenges

This abstract highlights NASA's OSSE framework, developed at the Global Modeling and Assimilation Office, which has become a widely adopted tool for evaluating the impact of new observations on weather forecasts. The framework involves simulating realistic observations by introducing errors to mimic real-world scenarios. By utilizing advanced radiative transfer modeling, the accuracy of simulated observations is significantly improved, enhancing the reliability of experimental outcomes. The talk focuses on recent progress and challenges in three key areas. Firstly, it explores the techniques used to simulate synthetic observations, a crucial aspect of OSSE experiments. Secondly, the presentation also discusses the challenges of examining the observation errors that need to be added to the perfect observations to generate realistic simulated observations. Lastly, the assimilation of synthetic observations and their impact on forecast skills is evaluated, providing valuable insights for optimizing current and future observing systems for improving the weather forecasts. By sharing recent advancements and acknowledging challenges, this presentation seeks to inspire researchers to leverage the OSSE framework in weather forecasting. NASA's OSSE techniques hold promise for a better understanding of the atmosphere and the development of more accurate and reliable weather predictions.

Isaac Moradi↗

High-Level Synthesis of Parallel Specifications Coupling Static and Dynamic Controllers

The increased need for efficient ways to implement domain-specific accelerators is driving design methodologies towards the use of abstractions higher than the Register Transfer Level (RTL). In this scenario, High Level Synthesis (HLS) plays a significant role by enabling the automatic generation of custom hardware accelerators starting from high level descriptions (e.g., C code). Conventional HLS tools exploit parallelism mostly at the Instruction Level (ILP). They statically schedule the input specifications, and build centralized Finite State Machine (FSM) controllers. However, aggressive exploitation of ILP in many applications has diminishing returns and, usually, centralized approaches do not efficiently exploit coarser parallelism because FSMs are inherently serial. In this paper we present a HLS framework able to synthesize applications that, beside ILP, also expose Task Level Parallelism (TLP). An application can expose TLP through annotations that identify the parallel functions (i.e., tasks). To generate accelerators that efficiently execute concur- rent tasks, we need to solve several issues: devise a mechanism to support concurrent execution flows, exploit memory parallelism, and manage synchronization. To support concurrent execution flows, we introduce a novel adaptive controller. The adaptive controller is composed of a set of interacting control elements that independently manage the execution of a single operation or function call. These control elements check dependencies and resource constraints at runtime, enabling as soon as possible execution. To support parallel access to shared memories and synchronization, we introduce a novel Hierarchical Memory Interface (HMI). With respect to previous solutions, the proposed interface supports multi-ported memories and atomic memory operations, which commonly occur in parallel programming. Our framework can generate the hardware implementation of C functions by employing two different approaches, depending on its characteristics. If a function exposes TLP, then the framework generates hardware implementations based on the adaptive controller. Otherwise, the framework implements the function by exploiting a more conventional FSM approach, which is optimized for ILP exploitation. We evaluate our framework on a set of parallel applications, and show substantial performance improvements (average speedup of 4.7) with limited area over- heads (average area increase of 5.48 times).

Castellana, Vito G.↗

High-Level Synthesis of Parallel Specifications Coupling Static and Dynamic Controllers

The increased need for efficient ways to implement domain-specific accelerators is driving design methodologies towards the use of abstractions higher than the Register Transfer Level (RTL). In this scenario, High Level Synthesis (HLS) plays a significant role by enabling the automatic generation of custom hardware accelerators starting from high level descriptions (e.g., C code). Conventional HLS tools exploit parallelism mostly at the Instruction Level (ILP). They statically schedule the input specifications, and build centralized Finite State Machine (FSM) controllers. However, aggressive exploitation of ILP in many applications has diminishing returns and, usually, centralized approaches do not efficiently exploit coarser parallelism because FSMs are inherently serial. In this paper we present a HLS framework able to synthesize applications that, beside ILP, also expose Task Level Parallelism (TLP). An application can expose TLP through annotations that identify the parallel functions (i.e., tasks). To generate accelerators that efficiently execute concur- rent tasks, we need to solve several issues: devise a mechanism to support concurrent execution flows, exploit memory parallelism, and manage synchronization. To support concurrent execution flows, we introduce a novel adaptive controller. The adaptive controller is composed of a set of interacting control elements that independently manage the execution of a single operation or function call. These control elements check dependencies and resource constraints at runtime, enabling as soon as possible execution. To support parallel access to shared memories and synchronization, we introduce a novel Hierarchical Memory Interface (HMI). With respect to previous solutions, the proposed interface supports multi-ported memories and atomic memory operations, which commonly occur in parallel programming. Our framework can generate the hardware implementation of C functions by employing two different approaches, depending on its characteristics. If a function exposes TLP, then the framework generates hardware implementations based on the adaptive controller. Otherwise, the framework implements the function by exploiting a more conventional FSM approach, which is optimized for ILP exploitation. We evaluate our framework on a set of parallel applications, and show substantial performance improvements (average speedup of 4.7) with limited area over- heads (average area increase of 5.48 times).

Castellana, Vito G.↗

Concepts to Automate Fluid Transfer Capability of Low Impact Docking System (LIDS)

The capability to transfer mass between spacecraft is necessary for many mission scenarios. Docking and berthing operations have enabled fluid, electrical, crew and equipment transfers to some degree on all manned space operations since the Gemini program. The Apollo program performed some sophisticated docking maneuvers to land men on the moon and return them safely to Earth. These programs primarily transferred crew, equipment, and pressurized atmosphere between docked spacecraft. The International Space Station (ISS) U.S. modules are connected by Common Berthing Mechanism (CBM) portals. They provide many feed-through ports for electrical, and fluid transfer between modules, as well as a large diameter crew and equipment tunnel. Fluid and electrical jumpers are manually installed after the CBM sealing surfaces have been securely mated to maintain the pressurized cabin environment. CBM berthing and subsequent fluid transfer capability requires a lengthy manual process involving an active interface that mates with a passive half. The Androgynous Peripheral Attach System (MAS) a Russian technology that docked the Russian Zarya module to Unity, or Node 1, is a more complex system that also is capable of fuel transfer, enabling refueling of the Russian re-boost engines on ISS. For several years, a Low Impact Docking System (LIDS) has been under development at Johnson Space Center (JSC). This docking technology has a requirement to be androgynous in order to allow the fabrication of a single configuration that can dock with all other LIDS units. It is desired to make electrical and fluid coupling mating an automated process to enable routine docking and undocking operations to support future exploration missions. It is envisioned that modular design and vehicle assembly will require an efficient LIDS for fuel, electrical, crew, and equipment transfer. Marshall Space Flight Center (MSFC) has joined the LIDS development effort and plans to employ fluid transfer concepts and technology from previous development programs, such as the Automated Fluid Interface System (AFIS) and the Ohital Fluid Transfer System (OFTS) that were developed and tested by MSFC. Orbital Expressderived robotic satellite servicing technology is scheduled to fly soon to demonstrate fluid transfer technology developed for the Air Force. This paper will compare known technology against possible fluid transfer requirements for LIDS to develop design strategies for automated fluid transfer.

Miernik, Janie H.↗

The insertion of human dynamics models in the flight control loops of V/STOL research aircraft. Appendix 2: The optimal control model of a pilot in V/STOL aircraft control loops

An overview is presented of research work focussed on the design and insertion of classical models of human pilot dynamics within the flight control loops of V/STOL aircraft. The pilots were designed and configured for use in integrated control system research and design. The models of human behavior that were considered are: McRuer-Krendel (a single variable transfer function model); and Optimal Control Model (a multi-variable approach based on optimal control and stochastic estimation theory). These models attempt to predict human control response characteristics when confronted with compensatory tracking and state regulation tasks. An overview, mathematical description, and discussion of predictive limitations of the pilot models is presented. Design strategies and closed loop insertion configurations are introduced and considered for various flight control scenarios. Models of aircraft dynamics (both transfer function and state space based) are developed and discussed for their use in pilot design and application. Pilot design and insertion are illustrated for various flight control objectives. Results of pilot insertion within the control loops of two V/STOL research aricraft (Sikorski Black Hawk UH-60A, McDonnell Douglas Harrier II AV-8B) are presented and compared against actual pilot flight data. Conclusions are reached on the ability of the pilot models to adequately predict human behavior when confronted with similar control objectives.

Zipf, Mark E.↗

Uncovering the Role of Hole Traps in Promoting Hole Transfer from Multiexcitonic Quantum Dots to Molecular Acceptors

The understanding of electronic dynamics in multiexcitonic quantum dots (QDs) is important for designing efficient systems useful in high power scenarios, such as solar concentrators and multielectron charge transfer. The multiple charge carriers within a QD can undergo undesired Auger recombination events, which rapidly annihilate carriers on picosecond time scales and generate heat from absorbed photons instead of useful work. Compared to the transfer of multiple electrons, the transfer of multiple holes has proven to be more difficult due to slower hole transfer rates. To probe the competition between Auger recombination and hole transfer in CdSe, CdS, and CdSe/CdS QDs of varying sizes, we synthesized a phenothiazine derivative with optimized functionalities for binding to QDs as a hole accepting ligand and for spectroscopic observation of hole transfer. Transient absorption spectroscopy was used to monitor the photoinduced absorption features from both trapped holes and oxidized ligands under excitation fluences where the averaged initial number of excitons in a QD ranged from ~1 to 19. We observed fluence-dependent hole transfer kinetics that last around 100 ps longer than the predicted Auger recombination lifetimes, and the transfer of up to 3 holes per QD. Theoretical modeling of the kinetics suggests that binding of hole acceptors introduces trapping states significantly different from those in native QDs passivated with oleate ligands. Holes in these modified trap states have prolonged lifetimes, which promotes the hole transfer efficiency. These results highlight the beneficial role of hole-trapping states in devising hole transfer pathways in QD-based systems under multiexcitonic conditions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗