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At least 667 records · Page 37

Capture of uncontrolled satellites - A flight demonstration

NASA is presently exploring concepts, systems, and devices for capturing uncontrolled or non-operational satellites. Understanding of this type capture involves development of requirements and options, analyses of approaches, and extensive ground simulations. The verification of an approach is expected to require flight demonstrations of the concepts and hardware to assure confidence in application. This paper addresses a flight demonstration involving the Shuttle, an Orbital Maneuvering Vehicle (OMV), a capture mechanism, and a target vehicle capable of providing characteristic motion. A mission scenario is projected which demonstrates a capture concept, mission sequencing, capture vehicle potential, and overall capture possibilities with man-in-the-loop control. The proposed demonstration is considered a stepping stone to more demanding capture requirements. On-orbit activities are deliberately constrained to existing technology and projected systems and hardware capability for the year 1990.

Lenox, H. M.↗

Autonomous and Autonomic Systems: A Paradigm for Future Space Exploration Missions

NASA increasingly will rely on autonomous systems concepts, not only in the mission control centers on the ground, but also on spacecraft and on rovers and other assets on extraterrestrial bodies. Automomy enables not only reduced operations costs, But also adaptable goal-driven functionality of mission systems. Space missions lacking autonomy will be unable to achieve the full range of advanced mission objectives, given that human control under dynamic environmental conditions will not be feasible due, in part, to the unavoidably high signal propagation latency and constrained data rates of mission communications links. While autonomy cost-effectively supports accomplishment of mission goals, autonomicity supports survivability of remote mission assets, especially when human tending is not feasible. Autonomic system properties (which ensure self-configuring, self-optimizing self-healing, and self-protecting behavior) conceptually may enable space missions of a higher order into any previously flown. Analysis of two NASA agent-based systems previously prototyped, and of a proposed future mission involving numerous cooperating spacecraft, illustrates how autonomous and autonomic system concepts may be brought to bear on future space missions.

Truszkowski, Walter F.↗

Considerations for Isochronous Data Services over the Proximity-1 Space Link

Future mission concepts for robotic and human explorations will involve a high level of real time control/monitoring operations such as tele-operation for spacecraft rendezvous and surface mobile platforms carrying life-support equipments. The timely dissemination of voice, command, and real-time telemetry for monitoring and coordination purposes is critical for mission success. It is envisioned that future missions will require a network infrastructure capable of supporting isochronous data services. The CCSDS Proximity-1 Space Link Protocol1 could be used to provide isochronous service over the surface-to-Earth relay as well as "beyond-the-horizon" communications between distant Lunar or Mars surface elements. This paper will analyze the latency, jitter, and throughput performance of the Proximity-1 protocol for isochronous applications. In particular we will focus on constrained scenarios where the protocol operates in full-duplex mode, carrying isochronous traffic in one direction and error-controlled traffic in the other direction. We analyze the impact of the strict priority scheme in Proximity-1 on delay jitter and the impact of the isochronous traffic on the efficiency of the reliable data transfer in the other direction, and discuss methods for performance optimization. In general, jitter performance is driving by relative loading of isochronous traffic on the forward link compared to the acknowledgement traffic. Under light loading condition, the upper-bound of the delay jitter is the transmission duration of an acknowledgement frame on the forward link; for higher loading scenarios, the maximum jitter is scaled up by the inverse of the residual bandwidth, i.e., the spare capacity available in the forward link to carry isochronous traffic.

isochronous communications↗

Considerations for Isochronous Data Services over the Proximity-1 Space Link

Future mission concepts for robotic and human explorations will involve a high level of real time control/monitoring operations such as tele-operation for spacecraft rendezvous and surface mobile platforms carrying life-support equipments. The timely dissemination of voice, command, and real-time telemetry for monitoring and coordination purposes is critical for mission success. It is envisioned that future missions will require a network infrastructure capable of supporting isochronous data services. The CCSDS Proximity-1 Space Link Protocol1 could be used to carry isochronous traffic. This paper we will focus on the data link layer portion of the Proximity-1 protocol specification and analyze its jitter and performance for supporting isochronous applications. In particular we will focus on constrained scenarios where the protocol operates in full-duplex mode, carrying isochronous traffic in one direction and error-controlled traffic in the other direction. We analyze the impact of the strict priority scheme in Proximity-1 used to arbitrate channel access on the latency jitter of the isochronous traffic and the efficiency of the reliable data transfer. In general, jitter performance is driven by the loading of the acknowledgement traffic on the forward link. Under light loading condition, the upper-bound of the delay jitter is the transmission duration of an acknowledgement frame on the forward link; for higher loading scenarios, the maximum jitter is scaled up by the inverse of the residual bandwidth, i.e., the spare capacity available in the forward link after accounting for the acknowledgement traffic. We derive analytical expression on the maximum jitter and discuss its performance.

space link↗

Medical System Concept of Operations for Mars Exploration Missions

Future exploration missions will be the first time humanity travels beyond Low Earth Orbit (LEO) since the Apollo program, taking us to cis-lunar space, interplanetary space, and Mars. These long-duration missions will cover vast distances, severely constraining opportunities for emergency evacuation to Earth and cargo resupply opportunities. Communication delays and blackouts between the crew and Mission Control will eliminate reliable, real-time telemedicine consultations. As a result, compared to current LEO operations onboard the International Space Station, exploration mission medical care requires an integrated medical system that provides additional in-situ capabilities and a significant increase in crew autonomy. The Medical System Concept of Operations for Mars Exploration Missions illustrates how a future NASA Mars program could ensure appropriate medical care for the crew of this highly autonomous mission. This Concept of Operations document, when complete, will document all mission phases through a series of mission use case scenarios that illustrate required medical capabilities, enabling the NASA Human Research Program (HRP) Exploration Medical Capability (ExMC) Element to plan, design, and prototype an integrated medical system to support human exploration to Mars.

Urbina, M.↗

Medical System Concept of Operations for Mars Exploration Missions

Future exploration missions will be the first time humanity travels beyond Low Earth Orbit (LEO) since the Apollo program, taking us to cis-lunar space, interplanetary space, and Mars. These long-duration missions will cover vast distances, severely constraining opportunities for emergency evacuation to Earth and cargo resupply opportunities. Communication delays and blackouts between the crew and Mission Control will eliminate reliable, real-time telemedicine consultations. As a result, compared to current LEO operations onboard the International Space Station, exploration mission medical care requires an integrated medical system that provides additional in-situ capabilities and a significant increase in crew autonomy. The Medical System Concept of Operations for Mars Exploration Missions illustrates how a future NASA Mars program could ensure appropriate medical care for the crew of this highly autonomous mission. This Concept of Operations document, when complete, will document all mission phases through a series of mission use case scenarios that illustrate required medical capabilities, enabling the NASA Human Research Program (HRP) Exploration Medical Capability (ExMC) Element to plan, design, and prototype an integrated medical system to support human exploration to Mars.

Urbina, Michelle↗

Toward an IMU-based Space Suit Motion Capture System

Spacesuits are complex engineering systems that sustain human health and enable performance outside of Earth-like environments. These systems must support human mobility and physical workload demands while minimizing injury risk during extravehicular activity (EVA). Future EVA on the lunar surface during the Artemis program is expected to be more frequent and require higher physical workloads than previous EVAs during the ISS, Shuttle, or Apollo programs. Hence it is important to optimize future as well as current spacesuits to be efficient and comfortable for the success of space and planetary missions. To enable this, an efficient method is needed to test these spacesuits on the ground.When testing spacesuits in ground environments, it is often necessary to understand the kinematics of the suit to validate the design against relevant requirements or characterize the physical workload necessary to operate the suit. This is a challenging task for traditional optical motion capture (OMC) approaches: suit-mounted OMC markers are easily occluded by the subject or environment and may become detached during testing. Controlling lighting and reflectivity of objects in the motion capture volume is also difficult. Fixed-position OMC cameras also constrain testing to a small and contrived laboratory environment, disallowing kinematics capture in field environments.One promising alternative is the use of suit-mounted inertial measurement units (IMUs). These sensors are small, unobtrusive, and portable, but come at the cost of increased sensor noise and complexity of the software and mathematics to analyze the collected data. To this end, engineers at NASA are developing the Augmented Suit Inverse Kinematics (ASIK) system, a complete motion capture methodand inverse kinematics solver which relies solely on a network of wireless IMUs attached to the major kinematic segments of the spacesuit. The ASIK modeling language allows for the simple inclusion of probabilistic priors such as suit size and shape or IMU positions and rotations. Furthermore, to increase accuracy and reduce operational overhead to use this motion capture approach, the developed inverse kinematics solver exploits so-called self-calibratingalgorithmic techniques, which reduce the need for precise alignment of the sensors on the segments or scripted functional calibration procedures. The ASIK system was tested in a 7-subject pilot study. Each subject donned NASA’s new prototype exploration spacesuit in the Active Response Gravity Offload System (ARGOS) facility at the NASA Johnson Space Center. The subjects were outfitted with a set of 14 APDM (Portland, OR, USA) Opal IMUs, 12 of which were used in the ASIK model to estimate lower body and trunk kinematics. The subjects were also outfitted with a set of reflective OMC markers and traditional OMC data was collected and processed. Presented results will include characterization of ASIK-derived suit joint angles accuracy against an optical motion capture datum. Discussion of these results, as well as discussion of system calibration and nuances of mathematical observability, will be included.If successful, IMU-based motion capture will enable testing and validation of spacesuits more frequently, with less overhead, in more extreme environments. Future work will apply these techniques to common spacesuit testing tasks, such as gait, mobility, and balance assessment, physical workload characterization, and ergonomics evaluations.

Timothy Mcgrath↗

Active Turbine Tip Clearance Control Trade Space Analysis of an Advanced Geared Turbofan Engine

Tip clearance within the high pressure turbine of a gas turbine engine is a significant factor in engine performance and efficiency. In the pursuit of higher efficiency, aero-engine designs are migrating toward compact gas turbine (CGT) technology that seeks to increase the bypass ratio of the gas turbine engine without increasing the size of the fan, which is constrained by its underwing location. The reduced size of CGTs invoke concern over increased sensitivity of engine performance due to turbine tip clearance gap that makes an argument for advanced tip clearance mitigation and control techniques to be employed. This paper evaluates the tip clearance trade space for a conceptual geared turbofan engine with a CGT core. This is accomplished through a modeling and simulation approach that includes a sensitivity analysis of engine performance in response to high pressure turbine tip clearance as well as an evaluation of the sensitivity of tip clearance to various design parameters, including material properties and component cooling characteristics. Also included is a parametric study of actuators that provides preliminary requirements for implementation of active turbine tip clearance control actuation systems. The results produced from these studies are meant to be informative, with special emphasis on the demonstration of a systematic approach. The modeling approach appears to capture expected trends. The studies suggest that the tip clearance gap will have a greater impact on the new CGT engines and that a relatively slow, actively controlled actuation system may be sufficient as long as it has control authority to both open and close the tip clearance gap.

tip clearance control↗

Air quality and comfort constrained energy efficient operation of multi-zone buildings

Maintaining indoor air quality (IAQ) through effective ventilation is essential for the well-being and productivity of building occupants. Control strategies aimed at improving the efficiency of heating, ventilation and air conditioning (HVAC) systems must jointly determine ventilation and heating and cooling processes. Here, in this paper, we study the problem of minimizing the energy consumption of the HVAC system in a multi-zone building, while meeting thermal comfort and IAQ requirements. We first perform a steady state analysis of the zonal carbon dioxide (CO 2 ) concentration and the temperature dynamics. The resulting expressions are convex in the zonal mass flow rates and zonal temperatures. Guided by the steady state solutions for meeting the thermal comfort constraints, we develop two control policies for improving the energy efficiency of building HVAC systems while jointly satisfying indoor temperature and IAQ constraints. We compare the performance of our proposed approaches with those of multiple baseline approaches which implement separate regimes for controlling zonal temperature and IAQ for a typical work-day in a multi-zone campus building. We have evaluated the performance of our proposed approaches under varying levels of flexibility in zonal temperatures. We have shown that zonal temperature flexibility can result in energy savings up to 32% (for the same control strategies) as compared to the case where no such flexibility is permitted. Our proposed approaches were seen to offer potential savings of nearly 29% compared to the baseline.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Experiments in Aircraft Roll-Yaw Control using Forebody Tangential Blowing

Advantages of flight at high angles of attack include increased maneuverability and lift capabilities. These are beneficial not only for fighter aircraft, but also for future supersonic and hypersonic transport aircraft during take-off and landing. At high angles of attack the aerodynamics of the vehicle are dominated by separation, vortex shedding and possibly vortex breakdown. These phenomena severely compromise the effectiveness of conventional control surfaces. As a result, controlled flight at high angles of attack is not feasible for current aircraft configurations. Alternate means to augment the control of the vehicle at these flight regimes are therefore necessary. The present work investigates the augmentation of an aircraft flight control system by the injection of a thin sheet of air tangentially to the forebody of the vehicle. This method, known as Forebody Tangential Blowing (FTB), has been proposed as an effective means of increasing the controllability of aircraft at high angles of attack. The idea is based on the fact that a small amount of air is sufficient to change the separation lines on the forebody. As a consequence, the strength and position of the vortices are altered causing a change on the aerodynamic loads. Although a very effective actuator, forebody tangential blowing is also highly non-linear which makes its use for aircraft control very difficult. In this work, the feasibility of using FTB to control the roll-yaw motion of a wind tunnel model was demonstrated both through simulations and experimentally. The wind tunnel model used in the experiments consists of a wing-body configuration incorporating a delta wing with 70-degree sweep angle and a cone-cylinder fuselage. The model is equipped with forebody slots through which blowing is applied. There are no movable control surfaces, therefore blowing is the only form of actuation. Experiments were conducted at a nominal angle of attack of 45 degrees. A unique apparatus that constrains the model to two degrees-of-freedom, roll and yaw, was designed and built. The apparatus was used to conduct dynamic experiments which showed that the system was unstable, its natural motion divergent. A model for the unsteady aerodynamic loads was developed based on the basic physics of the flow and results from flow visualization experiments. Parameters of the aerodynamic model were identified from experimental data. The model was validated using data from dynamic experiments. The aerodynamic model completes the equations of motion of the system which were used in the design of control laws using blowing as the only actuator. The unsteady aerodynamic model was implemented as part of the real-time vehicle control system. A control strategy using asymmetric blowing was demonstrated experimentally. A discrete vortex method was developed to help understand the main physics of the flow. The method correctly captures the interactions between forebody and wing vortices. Moreover, the trends in static loads and flow structure are correctly represented. Flow visualization results revealed the vortical structure of the flow to be asymmetric even for symmetric flight conditions. The effects of blowing, and roll and yaw angles on the flow structure were determined. It is shown that superimposing symmetric and asymmetric blowing has a linearizing effect on the actuator characteristics. Transient responses of roll and yaw moments to step input blowing were characterized, and their differences were explained based on the physical mechanisms through which these loads are generated.

Pedreiro, Nelson↗

Reactor Simulator Testing

As part of the Nuclear Systems Office Fission Surface Power Technology Demonstration Unit (TDU) project, a reactor simulator test loop (RxSim) was design & built to perform integrated testing of the TDU components. In particular, the objectives of RxSim testing was to verify the operation of the core simulator, the instrumentation and control system, and the ground support gas and vacuum test equipment. In addition, it was decided to include a thermal test of a cold trap purification design and a pump performance test at pump voltages up to 150 V since the targeted mass flow rate of 1.75 kg/s was not obtained in the RxSim at the originally constrained voltage of 120 V. This paper summarizes RxSim testing. The gas and vacuum ground support test equipment performed effectively in NaK fill, loop pressurization, and NaK drain operations. The instrumentation and control system effectively controlled loop temperature and flow rates or pump voltage to targeted settings. The cold trap design was able to obtain the targeted cold temperature of 480 K. An outlet temperature of 636 K was obtained which was lower than the predicted 750 K but 156 K higher than the cold temperature indicating the design provided some heat regeneration. The annular linear induction pump (ALIP) tested was able to produce a maximum flow rate of 1.53 kg/s at 800 K when operated at 150 V and 53 Hz. Keywords: fission, space power, nuclear, liquid metal, NaK.

Schoenfeld, Michael P.↗

Reactor Simulator Testing

As part of the Nuclear Systems Office Fission Surface Power Technology Demonstration Unit (TDU) project, a reactor simulator test loop (RxSim) was design & built to perform integrated testing of the TDU components. In particular, the objectives of RxSim testing was to verify the operation of the core simulator, the instrumentation and control system, and the ground support gas and vacuum test equipment. In addition, it was decided to include a thermal test of a cold trap purification design and a pump performance test at pump voltages up to 150 V since the targeted mass flow rate of 1.75 kg/s was not obtained in the RxSim at the originally constrained voltage of 120 V. This paper summarizes RxSim testing. The gas and vacuum ground support test equipment performed effectively in NaK fill, loop pressurization, and NaK drain operations. The instrumentation and control system effectively controlled loop temperature and flow rates or pump voltage to targeted settings. The cold trap design was able to obtain the targeted cold temperature of 480 K. An outlet temperature of 636 K was obtained which was lower than the predicted 750 K but 156 K higher than the cold temperature indicating the design provided some heat regeneration. The annular linear induction pump (ALIP) tested was able to produce a maximum flow rate of 1.53 kg/s at 800 K when operated at 150 V and 53 Hz.

Schoenfeld, Michael P.↗

Reactor Simulator Testing

As part of the Nuclear Systems Office Fission Surface Power Technology Demonstration Unit (TDU) project, a reactor simulator test loop (RxSim) was design & built to perform integrated testing of the TDU components. In particular, the objectives of RxSim testing was to verify the operation of the core simulator, the instrumentation and control system, and the ground support gas and vacuum test equipment. In addition, it was decided to include a thermal test of a cold trap purification design and a pump performance test at pump voltages up to 150 V since the targeted mass flow rate of 1.75 kg/s was not obtained in the RxSim at the originally constrained voltage of 120 V. This paper summarizes RxSim testing. The gas and vacuum ground support test equipment performed effectively in NaK fill, loop pressurization, and NaK drain operations. The instrumentation and control system effectively controlled loop temperature and flow rates or pump voltage to targeted settings. The cold trap design was able to obtain the targeted cold temperature of 480 K. An outlet temperature of 636 K was obtained which was lower than the predicted 750 K but 156 K higher than the cold temperature indicating the design provided some heat regeneration. The annular linear induction pump (ALIP) tested was able to produce a maximum flow rate of 1.53 kg/s at 800 K when operated at 150 V and 53 Hz.

Schoenfeld, Michael P.↗

Optimal Operation of a Hybrid Hydraulic Electric Architecture (HHEA) for Off-Road Vehicles Over Discrete Operating Decisions

Many off-highway machines including construction and agriculture equipment use hydraulics for power transmission and throttling as a means for control. Trends towards better efficiency and electrification have led to the creation of a novel Hybrid Hydraulic-Electric Architecture (HHEA) which could significantly reduce energy consumption and maintain control performance, even in machines that are too large to be directly electrified. This is achieved by using a set of common pressure rails to transmit the majority of power via power dense hydraulics and modulating the power with small electric motor-drives to achieve precise control. This paper proposes a computationally efficient method for computing the optimal sequence of pressure rail selections for the HHEA over finite drive cycles. This is useful for fairly comparing the novel architecture’s energy performance to existing architectures and for use in iterative optimal design of the architecture. The optimal control technique makes use of a static model of the architecture and losses. Constraints are enforced such that the drive cycle is repeatable. The constrained optimal operation is solved using a Lagrange multiplier technique that transforms the optimization into a small set of sub-problems by considering combinations of active constraints. Each of these sub-problems can be solved efficiently because loss calculations for all time steps can be computed in parallel. A case study of an off-road construction machine demon-strates that the HHEA reduces energy consumption by 2/3 compared to the baseline load sensing architecture.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Collaborative Arrival Planning: Data Sharing and User Preference Tools

Air traffic growth and air carrier economic pressures have motivated efforts to increase the flexibility of the air traffic management process and change the relationship between the air traffic control service provider and the system user. One of the most visible of these efforts is the U.S. government/industry "free flight" initiative, in which the service provider concentrates on safety and cross-airline fairness, and the user on their business objectives and operating preferences, including selecting their own path and speed in real-time. In the terminal arrival phase of flight, severe restrictions and rigid control are currently placed on system users, typically without regard for individual user operational preferences. Airborne delays applied to arriving aircraft into capacity constrained airports are imposed on a first-come, first-serve basis, and thus do not allow the system user to plan for or prioritize late arrivals, or to economically optimize their arrival sequence. A central tenant of the free-flight operating paradigm is collaboration between service providers and users in reaching air traffic management decisions. Such collaboration would be particularly beneficial to an airline's "hub" operation, where off-schedule arrival aircraft are a consistent problem, as they cause serious air-port ramp difficulties, rippling airline scheduling effects, and result in large economic inefficiencies. Greater collaboration can also lead to increased airport capacity and decrease the severity of over-capacity rush periods. In the NASA Collaborative Arrival Planning (CAP) project, both independent exchange of real-time data between the service provider and system user and collaborative decision support tools are addressed. Data exchange of real-time arrival scheduling, airspace management, and air carrier fleet data between the FAA service provider and an air carrier is being conducted and evaluated. Collaborative arrival decision support tools to allow intra-airline arrival preferences are being developed and simulated. The CAP project is part of and leveraged from the NASA/FAA Center TRACON Automation System (CTAS), a fielded set of decision support tools that provide computer generated advisories for both enroute and terminal area controllers to manage and control arrival traffic more efficiently. In this paper, the NASA Collaborative Arrival Planning project is outlined and recent results detailed, including the real-time use of CTAS arrival scheduling data by a major air carrier and simulations of tactical and strategic user preference decision support tools.

Zelenka, Richard E.↗

Reactor Simulator Integration and Testing

As part of the Nuclear Systems Office Fission Surface Power Technology Demonstration Unit (TDU) project, a reactor simulator (RxSim) test loop was designed and built to perform integrated testing of the TDU components. In particular, the objectives of RxSim testing were to verify the operation of the core simulator, the instrumentation and control system, and the ground support gas and vacuum test equipment. In addition, it was decided to include a thermal test of a cold trap purification design and a pump performance test at pump voltages up to 150 V because the targeted mass flow rate of 1.75 kg/s was not obtained in the RxSim at the originally constrained voltage of 120 V. This Technical Memorandum summarizes RxSim testing. The gas and vacuum ground support test equipment performed effectively in NaK fill, loop pressurization, and NaK drain operations. The instrumentation and control system effectively controlled loop temperature and flow rates or pump voltage to targeted settings. The cold trap design was able to obtain the targeted cold temperature of 480 K. An outlet temperature of 636 K was obtained, which was lower than the predicted 750 K but 156 K higher than the cold temperature, indicating the design provided some heat regeneration. The annular linear induction pump tested was able to produce a maximum flow rate of 1.53 kg/s at 800 K when operated at 150 V and 53 Hz.

Schoenfield, M. P.↗

3D seismic imaging of a fracture damage zone controlling reservoir compartmentalization at the Raft River EGS using multi-azimuth walkaway VSP

Accurate imaging of steeply dipping fracture zones in crystalline enhanced geothermal systems (EGS) is critical for constraining permeability architecture and guiding stimulation design. However, such structures remain poorly resolved by conventional surface seismic methods. We present a fully three-dimensional (3D) elastic-waveform inversion-migration workflow applied to multi-azimuth walkaway vertical seismic profiling (VSP) data acquired in a deviated borehole at the Raft River EGS. The workflow integrates first-arrival traveltime tomography, multi-scale elastic waveform inversion (EWI), and elastic least-squares reverse-time migration (ELSRTM) to recover high-resolution compressional-and shear-wave velocity models and to image structural discontinuities in the crystalline basement. The results reveal a laterally continuous low-velocity anomaly, with shear-wave velocity reductions of 25-30%, consistent with fractureinduced mechanical weakening. Two steeply dipping discontinuities bound a 50-80 m wide fracture damage zone. Independent constraints from microseismic clustering and geochemical compartmentalization corroborate the geometry and structural significance of this feature. Synthetic modeling further confirms that structures of this scale are resolvable (~30 m). These findings indicate that the Narrows structure is a distributed fracture damage zone rather than a discrete fault plane. By resolving fracture-zone geometry at the tens-of-meters scale using a single borehole, this workflow provides a practical and transferable approach for improving structural characterization, reducing uncertainty in permeability architecture, and supporting reservoir modeling and stimulation design in fractured crystalline EGS reservoirs.

58 GEOSCIENCES↗

Real-Space Constrained Density Functional Theory Investigation of Site-Specific, Interfacial Charge Recombination Dynamics Across the Au Nanoparticle/TiO 2 Heterojunction

Au nanoparticle (NP)/TiO 2 heterojunction is a representative system to study interfacial charge transfer in photocatalysis and photovoltaics, where suppressing recombination from TiO 2 to Au can enhance hot carrier extraction. We apply real-space constrained density functional theory (CDFT) with Marcus theory to quantify charge recombination time scales across Au/TiO 2 . This approach enables direct control and visualization of charge-separated states, aligning with site-specific probes like time-resolved X-ray photoelectron spectroscopy (trXPS). We find that the charge-separated state features a bipolaron, with recombination dominated by TiO 2 LUMO to Au HOMO transitions, primarily at interfacial Au sites. Marcus rate predictions are benchmarked with surface hopping methods, quantifying differences in time scales and computational efficiency. Lastly, we examine how the Au cluster size affects the free energy change (ΔG) and reorganization energy (λ), explaining trends in closed-shell systems and highlighting challenges for open-shell extrapolations. Overall, CDFT + Marcus theory provides efficient, mechanistically transparent interfacial charge transfer modeling, and we clearly defined its applicability and limitation.

Glenna, Drew M. [Univ. of Idaho, Idaho Falls, ID (↗