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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

CFD analysis of a solid pin-fueled small modular fluoride salt-cooled reactor

A computational fluid dynamics (CFD) study is performed for the pre-conceptual solid pin-fueled small modular fluoride salt-cooled reactor developed by the Oak Ridge National Laboratory (ORNL). The solid and fluid regions in a 1/12th section of a fuel assembly are modeled. The solid region includes fuel and non-fuel pins, with heat generation in the active region of the fuel pins. Two different power profiles, uniform and center-peaked, are considered. The FLiBe coolant flows from the bottom to the top of the core, parallel to the bank of fuel and non-fuel pins. The k-ω shear-stress transport (SST) model is chosen as the baseline turbulence model. The effects of grid refinement, inlet turbulence specification, and turbulence models on the temperature and pressure drop predictions are studied. Turbulence model sensitivity is investigated by comparing the results from the k-ω SST model with other two-equation models (k-ω baseline or BSL and k-ε realizable) as well as with anisotropic Reynolds stress transport models (linear pressure-strain and stress-BSL). Here the results show that the choice of turbulence model has a significant impact on the pin temperature and bundle pressure drop predictions. The results from the baseline turbulence model show good agreement between the fuel pin temperatures and bundle pressure drop values predicted using a subchannel model previously developed by the authors of the present study.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2021

Competitiveness Metrics for Electricity System Technologies

The relative economic competitiveness of power generation technologies is a topic of much interest to diverse electric industry participants. However, assessing competitiveness can be challenging as it requires considering both total costs and total system value of each technology, which are complicated by the (1) numerous and diverse grid services needed to operate a reliable power system; (2) variations in the economic value of the grid services with system state and location, and over multiple timescales, due to the challenges of transporting and storing electricity; and (3) the unique characteristics of different electric system assets. Ideally, metrics designed or used to convey technology competitiveness must consider these complexities, but existing metrics often fall short. For example, the levelized cost of energy does not consider the system economic value of the various technologies nor does it consider services beyond electricity production. Various other metrics have been designed with the purpose of more-accurately communicating the economic viability of electric system technologies. In this report, we summarize the primary sources and components of costs and value and review the known competitiveness metrics by presenting their definitions, applications, advantages, and disadvantages. We also introduce a new set of competitiveness metrics, which we refer to as System Profitability metrics, that more-directly applies the economic principles of return-on-investment to electric system technologies. We use conceptual examples to show how the System Profitability metrics better reflect economic viability and relative technology competitiveness compared with existing metrics. We also describe how competitiveness metrics can be quantified using optimization-based models and demonstrate this capability using a U.S. electric sector capacity expansion model.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Conceptual Design of Pulverized Coal Electricity Generating Units for Flexible Operation

This National Energy Technology Laboratory (NETL) study addresses the conceptual design of greenfield pulverized coal (PC) plants intended for flexible rather than high capacity factor baseload operation. The United States has plentiful, low-cost natural gas resources - studies of aggressive decarbonization scenarios of the US energy sector suggest that the variability of carbon-free power can be economically addressed using dispatchable natural gas-fueled generation. Globally, natural gas resources are not as plentiful or low cost; consequently, some regions of the world are anticipated to continue to rely upon coal generation, even as they pursue decarbonization efforts. To support the increased utilization of variable renewable generation in these coal-dependent regions, plant designs must target low-capacity factor coal plants with increased emphasis on flexibility attributes such as start-up times, ramp rates, minimum load, and part-load heat rates. While much work has been performed on the improvement of the flexibility for existing coal plants originally designed for baseload service, little public literature exists on clean sheet design for flexible operation. This conceptual design study aims to define the features, performance characteristics, and costs for greenfield coal plants intended for flexible operation. Quantifying these characteristics provides critical information required by utility owners, grid planners, energy market modelers, and energy policy decision makers in coal-dependent regions of the world to better understand how coal-fired power plants can support a transition to low carbon generation.

20 FOSSIL-FUELED POWER PLANTS↗
DOE OSTI2023

Open-Loop Control Co-Design of Semisubmersible Floating Offshore Wind Turbines Using Linear Parameter-Varying Models

Here, this paper discusses a framework to design elements of the plant and control systems for floating offshore wind turbines in an integrated manner using linear parameter-varying models. Multiple linearized models derived from aero-elastic simulation software in different operating regions characterized by the incoming wind speed are combined to construct an approximate low-fidelity model of the system. The combined model is then used to generate open-loop, optimal control trajectories as part of a nested control co-design strategy that explores the system’s power production and stability using the platform pitch tilt as a proxy in the context of crucial plant and control design decisions. The radial distance between the central and outer columns and the diameter of the outer columns of the semisubmersible platform are the plant design variables. The platform stability and power production are studied for different plant design decisions. The effect of plant decisions on subsequent power production and stability response of the floating wind turbine is quantified in terms of the levelized cost of energy. The results show that the inner-loop constraints and the plant design decisions affect the turbine’s power and, subsequently, the cost of the system.

17 WIND ENERGY↗
DOE OSTI2020

Scaling Laws of Exciton Recombination Kinetics in Low Dimensional Halide Perovskite Nanostructures

Carrier recombination is a crucial process governing the optical properties of a semiconductor. Although various theoretical approaches have been utilized to describe carrier behaviors, a quantitative understanding of the impact of defects and interfaces in low dimensional semiconductor systems is still elusive. Here, we develop a model system consisting of chemically tunable, highly luminescent halide perovskite nanocrystals to illustrate the role of carrier diffusion and material dimensionality on the carrier recombination kinetics and luminescence efficiency. Our advanced synthetic methods provide a well-controlled colloidal system consisting of nanocrystals with different aspect ratios, halide compositions, and surface conditions. Using this system, we reveal the scaling laws of photoluminescence quantum yield and radiative lifetime with respect to the aspect ratio of nanocrystals. The scaling laws derived herein are not only a phenomenological observation but proved a powerful tool disentangling the carrier dynamics of microscopic systems in a quantitative and interpretable manner. The investigation of our model system and theoretical formulation bring to light the dimensionality, as a hidden constraint on carrier dynamics, and identify the diffusion length as an important parameter that distinguishes nanoscale and macroscale carrier behaviors. Furthermore, the conceptual distinction in carrier dynamics in different dimensionality regimes informs new design rules for optical devices where complex microstructures are involved.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

LossLens: Diagnostics for Machine Learning Through Loss Landscape Visual Analytics

Modern machine learning often relies on optimizing a neural network's parameters using a loss function to learn complex features. Beyond training, examining the loss function with respect to a network's parameters (i.e., as a loss landscape) can reveal insights into the architecture and learning process. While the local structure of the loss landscape surrounding an individual solution can be characterized using a variety of approaches, the global structure of a loss landscape, which includes potentially many local minima corresponding to different solutions, remains far more difficult to conceptualize and visualize. To address this difficulty, we introduce LossLens, a visual analytics framework that explores loss landscapes at multiple scales. LossLens integrates metrics from global and local scales into a comprehensive visual representation, enhancing model diagnostics. Here we demonstrate LossLens through two case studies: visualizing how residual connections influence a ResNet-20, and visualizing how physical parameters influence a physics-informed neural network (PINN) solving a simple convection problem.

97 MATHEMATICS AND COMPUTING↗
DOE OSTI2026

Sensitivity of Next-Generation CMB Surveys to Neutrinos and Other Light Relics

Neutrinos and other light relics leave characteristic imprints in the cosmic microwave background anisotropies, making their observation a sensitive probe of the particle content and thermal history of the early universe. The energy density in these relativistic species is parameterized by their effective number $N_\mathrm{eff}$. Measuring this parameter at the percent level, which is a long-standing science goal of CMB-S4 and other experiments, would test a wide range of well-motivated physics within and beyond the Standard Model of particle physics. In this paper, we present Fisher-matrix forecasts of the projected sensitivity to $N_\mathrm{eff}$ of several CMB-S4 survey configurations considered during its extensive design phase. The conceptual design reaches $σ(N_\mathrm{eff}) < 0.03$ over its seven-year observing period, while the revised configuration achieves the same precision over a longer timescale. We complement these results with a cosmic-variance-limited survey over the same multipole range to quantify the room for improvement accessible with additional instrumental, observational, and theoretical efforts. Finally, we discuss the broad implications of precise $N_\mathrm{eff}$ measurements for the radiation sector, big bang nucleosynthesis, light thermal relics, and other early-universe physics. The forecasts presented in this work are performed with the publicly released DRAFT (Dark Radiation Anisotropy Flowdown Team) tool. It provides an end-to-end pipeline from simulated foreground maps and component separation to delensing and projected sensitivities for any cosmological parameter, and it can be directly applied to other cosmic microwave background survey designs.

Trendafilova, Cynthia [Case Western Reserve U., CE↗
DOE OSTI2026

Proliferated Resilient Economical Half-Meter Aperture Space Telescopes (PREEMPT)

The PREEMPT LDRD was motivated by a major national need for better space-based imaging systems that are both high performing and affordable for the US Government. Current optical payloads for intelligence, surveillance and reconnaissance (ISR) and space domain awareness (SDA) missions can cost hundreds of millions of dollars and take years to develop, which makes it difficult to build the large constellations required for persistent, world-wide coverage. To address this, the team aimed to advance a different kind of large-aperture (>25 cm) telescope, called a monolithic telescope, in which key optical surfaces are built into a single piece of fused silica. This design greatly reduces payload and spacecraft complexity, the need for precision focus actuators, improves mechanical and thermal robustness, and lowers cost when compared with traditional Cassegrain telescopes that rely on many precisely aligned components. The project focused on five primary thrusts. The first thrust was to advance the concept of a V10, 25 cm, monolithic telescope forward from optical design to flight-ready stage. This was accomplished in partnership with Optimax, who delivered the first test unit in the early stages of the LDRD. The team developed several technologies necessary for this optic to be integrated into a flight demonstration. These include carbon fiber housings, highly detailed structural and thermal models and stress-reducing elastic averaging Hirth groove designs. These technologies resulted in a successful maturation of the optic, which is now slated to fly in late 2026/early 2027 for a demonstration mission. The second thrust was to advance the manufacturability of these optics. In collaboration with NIF’s optical manufacturing shop, we reduced polishing time from 480 hours to 65 hours through the implementation of optimized processes and new tools. The NIF team utilized a conceptual V8 (18 cm) optic to demonstrate this optimization, though it can be applied to the rest of the monolithic optic portfolio. Third, the team developed the first conceptual V20 (50 cm) payload, which is slated to be the next generation of LLNL optical payload systems. A set of structural, dynamic and thermal simulations were performed to identify potential challenges in the future development of this payload. Early-stage simulations suggest the payload is feasible, though thermal management will be the key focus area to maintain optimal performance. Fourth, a non-linear model of Viton was developed, to further enhance the reliability of our structural and dynamic models for future payloads. Viton acts as the primary interface material between the optic and its housing. Lastly, the team focused on successfully displaying the feasibility of using additively manufactured metal composites for optical space payloads. The team successfully demonstrated layer by layer deposition of Al-SiC composites, which have highly tunable structural and coefficient of thermal expansion (CTE) properties. These are crucial for optical payloads because CTE mismatch is one of the causes for degraded optical performance for telescopes in orbit. Overall, the work showed that monolithic telescopes could become a practical, lower-cost path to high-resolution space imaging for both national security and scientific missions.

42 ENGINEERING↗
DOE OSTI2025

Strategy to safely enable X-ray computed tomography examination of highly radioactive tristructural isotropic nuclear fuel

Nondestructive post-irradiation examination of nuclear fuels and materials is useful in collecting data to inform commercial licensing of new nuclear concepts. This work details the planning, shielding design, and workflow of an X-ray computed tomography examination of an irradiated AGR-5/6/7 fuel compact with a dose rate of 1318 R/hr on contact from both β and ɤ-ray radiation with 120 R/hr of the dose rate coming exclusively from ɤ-rays. Post-irradiation examination of highly radioactive samples can help reduce the timeframe from conceptualization of novel nuclear concepts to their commercial implementation as not only is less time spent waiting for experiments to decay away to acceptable levels for examinations, but data from these experiments can more quickly inform model efforts and subsequent experiments. While this work represents the hottest radiological sample that has been openly transported and examined at Idaho National Laboratory’s Irradiated Materials Characterization Laboratory to date, it is anticipated that this work and its lessons learned will facilitate future examinations of similar or even more radioactive specimens.

42 - ENGINEERING↗
DOE OSTI2026

SoLID Program at JLab

An overview of the Solenoidal Large Intensity Device (SoLID) and its scientific program will be given in this talk. SoLID is a spectrometer/detector system proposed to exploit the full potential of the Jefferson Lab (JLab) 12 GeV energy upgrade. SoLID will push the limit of luminosity frontier in hadronic physics with its unique capability to handle very high rates with large acceptance under high luminosity (1037-39/cm2/s). A rich and vibrant scientific program has been developed for SoLID, including but not limited to the precision study of the 3d nucleon structure in both momentum space using Semi-Inclusive Deep Inelastic Scattering (SIDIS) and coordinate space using Deep Virtual Exclusive Reactions (DVER), probing physics beyond the Standard Model with Parity Violating Deep Inelastic Scattering (PVDIS), and investigating the gluonic field contribution to the proton structure and proton mass via J/¿ threshold production. The SoLID collaboration has developed a robust, low risk and flexible conceptual design, with a base line design capable of accomplishing its scientific goals and flexibility to adopt the cutting-edge technology. Detector subsystems have been tested with prototypes in realistic high luminosity conditions and are demonstrated to function well under extremely challenging environment to satisfy the requirements of planned experiments.

Chen, Jian-Ping [Thomas Jefferson National Acceler↗
DOE OSTI2023

Accelerating Nuclear Fuels and Materials Qualification by Multi-Level Irradiation Experiment Campaign

The advanced reactor technologies feature fuels, coolants, and materials that promise safer operating conditions under normal and accident scenarios. However, the nuclear fuels and materials qualifications require several decades (for example, new reactor fuel qualification from conceptualization requires about 20 years). Therefore, accelerating nuclear fuels and materials qualification is essential, and it can be achieved by combining high through-put materials irradiation and testing, advanced post-irradiation examinations, and Multiphysics modeling. This paper addressed the associated challenges in accelerating nuclear fuels and material qualification for new and advanced reactor designs, which differ based on fuel, coolant, operating conditions, and structural materials. These challenges vary for radiation level, operating conditions (e.g., temperature and pressure), and coolant type (e.g., corrosion environment). In addition, the challenges and limitations in modeling tools, experimental facilities, and licensing guidelines are also discussed, and a general solution path forward is recommended.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2023

Presentation: Accelerating Nuclear Fuels and Materials Qualification by Multi-Level Irradiation Experiment Campaign

The advanced reactor technologies feature fuels, coolants, and materials that promise safer operating conditions under normal and accident scenarios. However, the nuclear fuels and materials qualifications require several decades (for example, new reactor fuel qualification from conceptualization requires about 20 years). Therefore, accelerating nuclear fuels and materials qualification is essential, and it can be achieved by combining high through-put materials irradiation and testing, advanced post-irradiation examinations, and Multiphysics modeling. This paper addressed the associated challenges in accelerating nuclear fuels and material qualification for new and advanced reactor designs, which differ based on fuel, coolant, operating conditions, and structural materials. These challenges vary for radiation level, operating conditions (e.g., temperature and pressure), and coolant type (e.g., corrosion environment). In addition, the challenges and limitations in modeling tools, experimental facilities, and licensing guidelines are also discussed, and a general solution path forward is recommended.

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗
DOE OSTI2022

Computational Tools and Workflows for Quantitative Risk Assessment and Decision Support for Geologic Carbon Storage Sites: Progress and Insights from the U.S. DOE’s National Risk Assessment Partnership

The 2005 Intergovernmental Panel on Climate Change (IPCC) Special Report on CCS raised the profile of CO2 capture and storage (CCS) as an important technology for reducing greenhouse gas (GHG) emissions. CCS is now recognized as a key component of most climate change mitigation scenarios. Since publication of that report the international research, development, and deployment (RD&D) community has advanced key technical aspects, clarified regulatory requirements, explored value chain and infrastructure solutions, and developed incentive paradigms to enable and promote large-scale deployment of CCS. These efforts have included research to better characterize geologic storage resources, to improve injection performance and storage efficiency, to assess and manage subsurface environmental risks, and to advance monitoring technologies to assure system conformance. These efforts have helped to build confidence in the viability of geologic carbon storage (GCS), but stakeholder concerns about long-term risks and liability associated with GCS remain a hurdle to broad acceptance and large-scale deployment of CCS. Since 2010, the U.S. DOE’s National Risk Assessment Partnership (NRAP) – a research collaboration between five contributing national laboratories – has worked to establish and demonstrate methods and tools to quantify and manage the subsurface environmental risks associated with GCS, amidst uncertainty. This work supports the Office of Fossil Energy and Carbon Management Carbon Transport and Storage Program’s goal of advancing safe and secure commercial-scale GCS deployment. To address the technical challenge of simulating the physical response of the GCS site to large-scale CO2 injection, NRAP has adopted an approach that relies on coupling computationally efficient reduced-order and/or data-driven proxy models of important system components (i.e., storage reservoir, sealing caprock, leakage pathways, intermediate formations, overlying groundwater aquifers, and the atmosphere) in integrated assessment framework. That integrated model of the physical system is complemented with fit-for purpose functionality to support site characterization and risk-related decisions. The recently released NRAP Phase II toolset includes the Open-Source Integrated Assessment Model (NRAP-Open-IAM) for evaluation of trends in leakage risk and potential impact, tools to support monitoring design optimization (Designs for Risk Evaluation and Management – DREAM v3.0 and Passive Seismic Monitoring Tool - PSMT), and tools for state of stress evaluation (State-of-Stress Analysis Tool - SOSAT) and forecasting induced seismicity risk. The NRAP team has also released a pair of reports describing conceptual workflows to incorporate physics-based, quantitative risk assessment into many of the design, planning, operation, and closure decisions for GCS projects. An online catalogue highlights published studies where these tools and methods are demonstrated. In this presentation, the utility of these products to assess risks and address key stakeholder questions will be highlighted through examples, and related insights about the safety and security of geologic carbon storage in qualified storage sites will be discussed. The prospect of rapid, large-scale deployment of GCS technology to aggressively reduce anthropogenic CO2 emissions requires careful consideration of interference between multiple commercial-scale storage projects within a basin. Going forward, NRAP is expanding and adapting site-scale risk quantification tools and methods to enable assessment of risks and inform management decisions for basin-scale deployment. Increasingly, this work will leverage next-generation approaches for surrogate modelling, fast prediction, and advanced visualization enabled by machine learning and artificial intelligence to promote virtual learning, scenario evaluation, and augment risk-based decision making.

quantitative risk assessment, geologic carbon stor↗
DOE OSTI2023

Safeguards Facility Model for Lead-cooled and Gas-cooled Fast Reactors

Efforts have been underway for many years on the development of safeguards for fast neutron reactors. The efforts have been primarily for sodium-cooled fast reactors (SFRs) in cooperation with Japan, to properly implement these safeguards as the reactors are conceptualized and ultimately commercialized. The primary challenge to development of adequate safeguard approaches for fast reactors has been in understanding how to apply different aspects of safeguards when facilities widely vary from one type of fast reactor to another and is largely dependent on several key aspects of the specific reactor type. For this report, the following key areas were identified for further analysis to determine where Lead-cooled Fast Reactors (LFRs) and Gas-Cooled Fast Reactors (GCFR) fuel material flow and key measurement points would differ from previously studied SFR safeguards.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗
DOE OSTI2022

Advancing river corridor science beyond disciplinary boundaries with an inductive approach to catalyse hypothesis generation

Abstract A unified conceptual framework for river corridors requires synthesis of diverse site‐, method‐ and discipline‐specific findings. The river research community has developed a substantial body of observations and process‐specific interpretations, but we are still lacking a comprehensive model to distill this knowledge into fundamental transferable concepts. We confront the challenge of how a discipline classically organized around the deductive model of systematically collecting of site‐, scale‐, and mechanism‐specific observations begins the process of synthesis. Machine learning is particularly well‐suited to inductive generation of hypotheses. In this study, we prototype an inductive approach to holistic synthesis of river corridor observations, using support vector machine regression to identify potential couplings or feedbacks that would not necessarily arise from classical approaches. This approach generated 672 relationships linking a suite of 157 variables each measured at 62 locations in a fifth order river network. Eighty four percent of these relationships have not been previously investigated, and representing potential (hypothetical) process connections. We document relationships consistent with current understanding including hydrologic exchange processes, microbial ecology, and the River Continuum Concept, supporting that the approach can identify meaningful relationships in the data. Moreover, we highlight examples of two novel research questions that stem from interpretation of inductively‐generated relationships. This study demonstrates the implementation of machine learning to sieve complex data sets and identify a small set of candidate relationships that warrant further study, including data types not commonly measured together. This structured approach complements traditional modes of inquiry, which are often limited by disciplinary perspectives and favour the careful pursuit of parsimony. Finally, we emphasize that this approach should be viewed as a complement to, rather than in place of, more traditional, deductive approaches to scientific discovery.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

A New Post‐Hoc Method to Reduce the Energy Imbalance in Eddy Covariance Measurements

Abstract Latent and sensible heat flux observations are essential for understanding land–atmosphere interactions. Measurements from the eddy covariance technique are widely used but suffer from systematic energy imbalance problems, partly due to missing large eddies from sub‐mesoscale transport. Because available energy drives the development of large eddies, we propose an available energy based correction method for turbulent flux measurements. We apply our method to 172 flux tower sites and show that we can reduce the energy imbalance from −14.99 to −0.65 W m −2 on average, together with improved consistency between turbulent fluxes and available energy and associated increases inr 2 at individual sites and across networks. Our results suggest that our method is conceptually and empirically preferable over the method implemented in the ONEFlux processing. This can contribute to the efforts in understanding and addressing the energy imbalance issue, which is crucial for the evaluation and calibration of land surface models.

Geology↗
DOE OSTI2021

Conceptual Design of Temperature-Controlled Fueled-Salt Irradiation Experiment to Support Demonstration of Advanced Nuclear Reactors

The irradiation testing of fuel-bearing molten salts is critical to supporting the development and demonstration of molten salt reactors (MSRs). These experiments can inform several important reactor design and safety parameters, including source term modeling, evolution of thermophysical properties with burn-up, and the degradation of structural materials under reactor relevant conditions. Idaho National Laboratory is designing an instrumented and heated high temperature molten salt-fueled irradiation capsule to study the behavior of the fuel salt during in-pile irradiation. This paper details the neutronics, thermal, and mechanical analysis performed to-date. Parametric studies are performed to assess a range of material, different experiment dimensions, two in-reactor positions, and the fuel enrichment used. Principal recommendations are to opt for a peripheral reactor position to alleviate neutronic constraints, a thin salt annulus to alleviate thermal constraints, and high-temperature alloys that provide additional safety margins.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2022

[Fe 4 S 4 ] cubane in sulfite reductases: new insights into bonding properties and reactivity

The dissimilatory sulfite reductase enzyme has very characteristic active site where the substrate binds to an iron site, ligated by a siroheme macrocycle and a thiol directly connected to a [Fe 4 S 4 ] cluster. This arrangement gives the enzyme remarkable efficiency in reducing sulfite and nitrite all the way to hydrogen sulfide and ammonia. For the first time we present a theoretical study where substrate binding modalities and activation are elucidated using active site models containing proton supply side chains and the [Fe 4 S 4 ] cluster. Density functional theory (DFT) was deployed in conjunction with the energy decomposition scheme (as implemented in AMS), the quantum theory of atoms in molecules (QTAIM), and conceptual DFT (cDFT) descriptors. We quantified the role of the electrostatic interactions inside the active site created by the side chains as well as the influence of the [Fe4S4] cluster on the substrate binding. Furthermore, using conceptual DFT results we shed light of the activation process, thus, laying foundation for further mechanistic studies. We found that the bonding of the ligands to the iron complex is dominated by electrostatic interactions, but the presence of the [Fe 4 S 4 ] cubane leads to substantial changes in electronic interaction. The spin state of the cubane, however, affects the binding energy only marginally. The conceptual DFT results show that the presence of the [Fe 4 S 4 ] cubane affects the reactivity of the active site as it is involved in electron transfer. This is corroborated by an increase in the electrophilicity index, thus making the active site more prone to react with the ligands. The interaction energies between the ligand and the siroheme group are also increased upon the presence of the cubane group, thus, suggesting that the siroheme group is not an innocent spectator but plays an active role in the reactivity of the dSIR active site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗