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DOE OSTI2025

Coherency-Constrained Spectral Clustering for Power Network Reduction

This paper presents a methodology for reducing the complexity of large-scale power network models using spectral clustering, aggregation of electrical components, and cost function approximation. Two approaches are explored using unconstrained and constrained spectral clustering to determine areas for effective system reduction. Once the system areas are determined, both loads and generators by type are aggregated, and their new cost function is approximated through polynomial curve-fitting or statistical methods. The performance of reduced networks is evaluated in terms of their ability to follow the true daily cost of the original system over a 24-hour period considering a set of several days. Two test systems are taken as test beds. Application of the methodology to a modified version of the IEEE 39-bus system reduces it from 17 generators to a 4-bus system and 9 generators with about 93% of accuracy. Similarly, the IEEE 118-bus system is reduced from 19 generators to a 3-bus system with three aggregated units achieving over 99% of accuracy. These findings address scalability challenges and enhance accuracy for high and mid-loading level conditions, and by aggregating thermal units with similar cost functions.

42 ENGINEERING↗

DOE OSTI2021

Single-Site Metal Organic Complexes on Oxide Supports for Selective Alkane Functionalization

High levels of reaction selectivity for heterogeneous catalysis are generally difficult to achieve with traditional metal nanoparticle catalysts, due to the variety of metal binding sites available. In this project, we have developed a metal-ligand coordination strategy to form transition metal single-sites on high surface area supports as heterogeneous single-site catalysts. Metal centers can be atomically dispersed in the binding pockets of organic ligands on oxide supports. The systems have to be carefully designed so that tendencies for metal cluster formation or binding to surface defect sites are overcome by the attractive coordination environment provided by the organic ligand. This was confirmed by a comprehensive set of characterization methods, including XAS, XPS, XRD, TEM, and CO adsorption. Design and tuning of metal-support and support-ligand interactions were crucial for high structural uniformity. We demonstrate that supported metal-ligand SSCs are effective, recyclable catalysts for alkene hydrosilylation reactions. Compared with commercial homogeneous catalysts, they exhibit improved yield and selectivity, less metal aggregation and side reactions, and stronger tolerance with functionalized substrates. These results give some preliminary indication that coordination with organic ligands can improve activity and selectivity in metal/oxide heterogeneous catalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2022

Underwater Noise Measurements around a Tidal Turbine in a Busy Port Setting

Acoustic emissions from current energy converters remain an environmental concern for regulators because of their potential effects on marine life and uncertainties about their effects stemming from a lack of sufficient observational data. Several recent opportunities to characterize tidal turbine sound emissions have begun to fill knowledge gaps and provide a context for future device deployments. In July 2021, a commercial-off-the-shelf hydrophone was deployed in a free-drifting configuration to measure underwater acoustic emissions and characterize a 25 kW-rated tidal turbine at the University of New Hampshire’s Living Bridge Project in Portsmouth, New Hampshire. Sampling methods and analysis were performed in alignment with the recently published IEC 62600-40 Technical Specification for acoustic characterization of marine energy converters. Results from this study indicate acoustic emissions from the turbine were below ambient sound levels and therefore did not have a significant impact on the underwater noise levels of the project site. As a component of Pacific Northwest National Laboratory’s Triton Field Trials (TFiT) described in this Special Issue, this effort provides a valuable use case for the IEC 62600-40 Technical Specification framework and further recommendations for cost-effective technologies and methods for measuring underwater noise at future current energy converter project sites.

tidal turbine↗

NASA NTRS1987

A general method for dynamic analysis of structures overview

The presented research deals with the development of a dynamic analysis method for structural systems. The modeling approach is essentially a finite element method in the sense that the structure is divided into n elements. An element is defined as any structural unit whose degree of freedom (dofs) can be categorized as either interface or non-interface dofs. An element could be a fundamental unit such as a rod, a beam, a plate etc., or it could be an entire structural component. Furthermore, the parameters for the element could be distributed or lumped. The choice of elements is totally arbitrary and is a matter of user convenience. In particular, issues of accuracy and convergence do not enter on the level of example that bookkeeping is reduced to a minimum. Each element is modeled using a set of interface constraint modes (ICM) combined with a set of interface restrained normal models (IRNM). The next step is the solution of the system eigenvalue problem. The procedure calls for the sequential solution of a number of small eigenvalue problems based on a truncation principle for IRNM. In addition, the form of these eigenvalue problems is very simple such that an escalator type of eigenvalue problem solver can be used which is extremely cost-effective and fast.

Engels, Remi C.↗

NASA NTRS2006

Strict Constraint Feasibility in Analysis and Design of Uncertain Systems

This paper proposes a methodology for the analysis and design optimization of models subject to parametric uncertainty, where hard inequality constraints are present. Hard constraints are those that must be satisfied for all parameter realizations prescribed by the uncertainty model. Emphasis is given to uncertainty models prescribed by norm-bounded perturbations from a nominal parameter value, i.e., hyper-spheres, and by sets of independently bounded uncertain variables, i.e., hyper-rectangles. These models make it possible to consider sets of parameters having comparable as well as dissimilar levels of uncertainty. Two alternative formulations for hyper-rectangular sets are proposed, one based on a transformation of variables and another based on an infinity norm approach. The suite of tools developed enable us to determine if the satisfaction of hard constraints is feasible by identifying critical combinations of uncertain parameters. Since this practice is performed without sampling or partitioning the parameter space, the resulting assessments of robustness are analytically verifiable. Strategies that enable the comparison of the robustness of competing design alternatives, the approximation of the robust design space, and the systematic search for designs with improved robustness characteristics are also proposed. Since the problem formulation is generic and the solution methods only require standard optimization algorithms for their implementation, the tools developed are applicable to a broad range of problems in several disciplines.

Crespo, Luis G.↗

NASA NTRS2012

Simple Cell Balance Circuit

A method has been developed for continuous cell voltage balancing for rechargeable batteries (e.g. lithium ion batteries). A resistor divider chain is provided that generates a set of voltages representing the ideal cell voltage (the voltage of each cell should be as if the cells were perfectly balanced). An operational amplifier circuit with an added current buffer stage generates the ideal voltage with a very high degree of accuracy, using the concept of negative feedback. The ideal voltages are each connected to the corresponding cell through a current- limiting resistance. Over time, having the cell connected to the ideal voltage provides a balancing current that moves the cell voltage very close to that ideal level. In effect, it adjusts the current of each cell during charging, discharging, and standby periods to force the cell voltages to be equal to the ideal voltages generated by the resistor divider. The device also includes solid-state switches that disconnect the circuit from the battery so that it will not discharge the battery during storage. This solution requires relatively few parts and is, therefore, of lower cost and of increased reliability due to the fewer failure modes. Additionally, this design uses very little power. A preliminary model predicts a power usage of 0.18 W for an 8-cell battery. This approach is applicable to a wide range of battery capacities and voltages.

Johnson, Steven D.↗

DOE OSTI2023

Unbalanced Nested Random Effects Estimation of Variance Components

To investigate the contributing factors of variance in the measurement of an iodine 127 (127I) sample, we implement a nested random effects analysis of variance (ANOVA). Historically, the reported uncertainty on a measurement of 127I has been obtained by methods of forward uncertainty propagation because there is typically only one replicate of a given sample for which to estimate the uncertainty. When samples are processed there are several types of quality control (QC) standards analyzed along-side the unknown samples with two to five replicates for each. Assuming the variance observed in these replicate QC standards is representative of that of the unknown samples, we use these data in a nested random effects ANOVA to estimate the total uncertainty of a measurement. We demonstrate this approach with two sets of measurements from Idaho National Laboratory and compare the results with the forward uncertainty propagation approach. Variance component estimates for the coarsest level of the nesting structure were most imprecise because replicates were most limited at these levels. We find that the results largely agree between forward propagation and ANOVA, and the greatest contributors of variance are due to instrument variation and chemical processing, with human processing being among the smallest contributors. This analysis provides reassurance that the reported uncertainties using forward propagation are reasonable and the process is well controlled. We propose a future designed experiment to increase replicates at the coarsest level of the hierarchy to improve estimates of these variance components.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2020

Scalable line and plane relaxation in a parallel structured multigrid solver

The efficient solution of sparse, linear systems that arise through the discretization of partial differential equations remains a key challenge for a range of high performance scientific simulations. One approach for reducing data movement and improving performance is by exposing and exploiting structure in a problem through the use of robust structured multilevel solvers. By choosing coarsening that preserves the structure of the problem, these methods maintain efficient structured computation and communication throughout the multigrid hierarchy. However, when coarsening is not permitted to be dependent on the operator, anisotropy must be addressed by the smoother — producing error compatible for coarse-grid correction with structured coarsening. Here, the components required in a scalable parallel structured solver are described with a focus on memory and communication efficiency of robust smoothers. While the implementation of communication and memory reduction techniques in smoothers integrated in a complete 3D solver present a significant engineering challenge, a novel approach is proposed that addresses these challenges systematically through a change to the solver’s execution model. Enabled by user-level threading paired with a set of data and communication abstractions, this approach permits seamless aggregation of communication in plane smoothers — directly reusing code for a 2D distributed multilevel cycle. Results show an effective reduction in communication costs for coarse-grid problems, and result in a speedup of 8.7x in smoothing routines shown in Fig. 12 using this approach. This produces a significant improvement to strong scalability while maintaining favorable weak scaling behavior. Finally, a parallel scaling study using a series of refined meshes is included that demonstrates the effectiveness of this approach in an application of interest.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2023

A Technology Roadmap for Advanced Geothermal Well Construction

Recent analysis has shown that by 2050, geothermal energy can supply up to 90 GW of power to the U.S. electrical grid. Reducing the lifecycle cost of geothermal wells is critical to achieving this level of adoption. While time-related costs of drilling remain an important issue, there is also a need to focus on the costs associated with casing and cementing of geothermal wells. This report provides a roadmap of R&D activities needed to reduce the life cycle cost of casing and cementing while improving life-of-well performance. The purpose of the roadmap is to develop priorities for R&D in the areas of (1) high-performance and cost-effective materials for target geothermal well conditions, (2) well construction methods and techniques to reduce construction costs, and (3) methods and techniques to decrease to decrease long-term operating costs. The roadmap sets targets for the next 10-year period and purposely excludes R&D efforts into improved rock reduction. The roadmap was developed by a joint working group of experts from Oak Ridge National Laboratory, Brookhaven National Laboratory, and Sandia National Laboratories as well as 35 experts from industry and academia. Input from a series of information gathering sessions was used to inform and guide the development of the roadmap.

15 GEOTHERMAL ENERGY↗

NASA NTRS2011

Evapotranspiration as a Regional Climate Priority: Results from a NASA/USDA Workshop

On April 5 to 7, 2011, the National Aeronautics and Space Administration (NASA) and the United States Department of Agriculture-Agricultural Research Service (USDA-ARS) sponsored a Workshop on Evapotranspiration (ET) in Silver Spring Maryland. The workshop was a response to a recommendation in the 2009-2011 GEO (Group on Earth Observations) Work Plan that a workshop on ET should be held to discuss issues related to ET products and services and the potential for incorporating ET activities into the 2012-2015 GEO Work Plan. The workshop had a regional emphasis, although there were several excellent international and global presentations including one on the GEWEX LANDFLUX project. The different scales of these activities suggests that a framework is needed that can accommodate both regional and global ET activities. Despite limitations with the workshop's scheduling, it attracted 76 experts who contributed informative presentations and insightful discussions. The goals of the workshop involved the exchange of information and ideas and the development of plans for providing more visibility for ET issues. Specific objectives included 1) defining the needs and requirements for evapotranspiration data in weather and climate studies, in natural and agro-ecoystem monitoring, and in water resource management; 2) reviewing the methods used to measure and model evapotranspiration; 3) assessing surface and satellite observation systems required to support ET measurement, modeling and evaluation; 4) assessing the feasibility of developing a proposal for a task on evapotranspiration for the 2012-2015 GEO Work Plan, and 5) exploring the level of support and consensus for developing a strategy for establishing evapotranspiration as an Essential Climate Variable (ECV) within the Global Climate Observing System (GCOS) framework The workshop featured a combination of oral presentations and breakout group sessions focused on the above objectives. There were also poster presentations providing opportunities for one-on-one discussions of ET modeling and measurement techniques. Presentations by users of ET data set the tone for the workshop. In the USA at the national and regional levels water rights issues represent a major opportunity for ET applications. ET data play a major role in estimating water loss due to irrigation, the largest cause of consumptive water loss in the USA, particularly in the West. Irrigation requirements are relatively specific since the needs are clearly defined by the geometry and number of the irrigation systems and can be monitored with high resolution satellite data. There was a strong consensus that land surface temperature (LST) at high resolution is critical for monitoring irrigation. State governments have made commitments to more efficient water management in the western US, but they need full access to improved and more timely ET data and applications to implement this plan. Water managers also reported that in spite of the recent development of. new techniques, the procedures used in some of the water balance calculations in some states are out of date and do not take advantage of new observational and data assimilation systems. The development of ET forecasts for water management is also seen as a priority. Although ET forecasts are currently being produced on an experimental basis these predictions could be improved by considering ET as a dynamic prediction variable in models and by increasing the time resolution of these ET predictions.

Lawford, Richard↗

NASA NTRS2011

Initiating Molecular Growth in the Interstellar Medium via Dimeric Complexes of Observed Ions and Molecules

A feasible initiation step for particle growth in the interstellar medium (ISM) is simulated by means of ab quantum chemistry methods. The systems studied are dimer ions formed by pairing nitrogen containing small molecules known to exist in the ISM with ions of unsaturated hydrocarbons or vice versa. Complexation energies, structures of ensuing complexes and electronic excitation spectra of the encounter complexes are estimated using various quantum chemistry methods. Moller-Plesset perturbation theory (MP2, Z-averaged perturbation theory (ZAP2), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)), and density functional theory (DFT) methods (B3LYP) were employed along with the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Two types of complexes are predicted. One type of complex has electrostatic binding with moderate (7-20 kcal per mol) binding energies, that are nonetheless significantly stronger than typical van der Waals interactions between molecules of this size. The other type of complex develops strong covalent bonds between the fragments. Cyclic isomers of the nitrogen containing complexes are produced very easily by ion-molecule reactions. Some of these complexes show intense ultraviolet visible spectra for electronic transitions with large oscillator strengths at the B3LYP, omegaB97, and equations of motion coupled cluster (EOM-CCSD) levels. The open shell nitrogen containing carbonaceous complexes especially exhibit a large oscillator strength electronic transition in the visible region of the electromagnetic spectrum.

Bera, Partha P.↗

NASA NTRS2013

Probabilistic Analysis for Comparing Fatigue Data Based on Johnson-Weibull Parameters

Leonard Johnson published a methodology for establishing the confidence that two populations of data are different. Johnson's methodology is dependent on limited combinations of test parameters (Weibull slope, mean life ratio, and degrees of freedom) and a set of complex mathematical equations. In this report, a simplified algebraic equation for confidence numbers is derived based on the original work of Johnson. The confidence numbers calculated with this equation are compared to those obtained graphically by Johnson. Using the ratios of mean life, the resultant values of confidence numbers at the 99 percent level deviate less than 1 percent from those of Johnson. At a 90 percent confidence level, the calculated values differ between +2 and 4 percent. The simplified equation is used to rank the experimental lives of three aluminum alloys (AL 2024, AL 6061, and AL 7075), each tested at three stress levels in rotating beam fatigue, analyzed using the Johnson- Weibull method, and compared to the ASTM Standard (E739 91) method of comparison. The ASTM Standard did not statistically distinguish between AL 6061 and AL 7075. However, it is possible to rank the fatigue lives of different materials with a reasonable degree of statistical certainty based on combined confidence numbers using the Johnson- Weibull analysis. AL 2024 was found to have the longest fatigue life, followed by AL 7075, and then AL 6061. The ASTM Standard and the Johnson-Weibull analysis result in the same stress-life exponent p for each of the three aluminum alloys at the median, or L(sub 50), lives

Vlcek, Brian L.↗

NASA NTRS2013

Carbon Dioxide: Surprising Effects on Decision Making and Neurocognitive Performance

The occupants of modern submarines and the International Space Station (ISS) have much in common as far as their air quality is concerned. Air is polluted by materials offgassing, use of utility compounds, leaks of systems chemicals, and anthropogenic sources. The primary anthropogenic compound of concern to submariners and astronauts has been carbon dioxide (CO2). NASA and the US Navy rely on the National Research Council Committee on Toxicology (NRC-COT) to help formulate exposure levels to CO2 that are thought to be safe for exposures of 3-6 months. NASA calls its limits Spacecraft Maximum Allowable Concentrations (SMACs). Years of experience aboard the ISS and a recent publication on deficits in decision making in ground-based subjects exposed briefly to 0.25% CO2 suggest that exposure levels that have been presumed acceptable to preserve health and performance need to be reevaluated. The current CO2 exposure limits for 3-6 months set by NASA and the UK Navy are 0.7%, and the limit for US submariners is 0.5%, although the NRC-COT recommended a 90-day level of 0.8% as safe a few years ago. NASA has set a 1000-day SMAC at 0.5% for exploration-class missions. Anecdotal experience with ISS operations approaching the current 180-day SMAC of 0.7% suggest that this limit is too high. Temporarily, NASA has limited exposures to 0.5% until further peer-reviewed data become available. In the meantime, a study published last year in the journal Environmental Health Perspectives (Satish U, et al. 2012) demonstrated that complexdecision- making performance is somewhat affected at 0.1% CO2 and becomes "dysfunctional" for at least half of the 9 indices of performance at concentrations approaching 0.25% CO2. The investigators used the Strategic Management Simulation (SMS) method of testing for decisionmaking ability, and the results were so surprising to the investigators that they declared that their findings need to be independently confirmed. NASA has responded to the findings on decision making by developing a study to either confirm or refute the published results. In addition, other neurocognitive tests that have been and will be used aboard the ISS will be part of the ground-based study. Further evaluations during the exposures will include ocular and cardiovascular effects of CO2 exposure. In addition, the 1- carbon genetics of the test subjects will be evaluated to determine if any individual subjects are unusually susceptible to CO2 exposure because of genetic factors. Our plan is to extend the published study from Satish by employing a wider series of CO2 exposures to include concentrations of 0.06, 0.12, 0.25, and 0.50%. We believe that our findings will be of keen interest to submariners and to those designing "tight" buildings.

James, John T.↗

DOE OSTI2021

A Load Switching Group based Feeder-level Microgrid Energy Management Algorithm for Service Restoration in Power Distribution System

This paper presents a load switching group based energy management system (LSG-EMS) for operating microgrids on a distribution feeder powered by one or multiple grid-forming distributed energy resources. Loads on a distribution feeder are divided into load switching groups that can be remotely switched on and off. The LSG-EMS algorithm, formulated as a mixed-integer linear programming (MILP) problem, has an objective function of maximizing the served loads while minimizing the total number of switching actions. A new set of topology constraints are developed for allowing multiple microgrids to be formed on the feeder and selecting the optimal supply path. Customer comfort is accounted for by maximizing the supply duration in the customer preferred service period and enforcing a minimum service duration. The proposed method is demonstrated on a modified IEEE 33-bus system using actual customer data. Simulation results show that the LSG-EMS successfully coordinates multiple grid-forming sources by selecting an optimal supply topology that maximizes the supply period of both the critical and noncritical loads while minimizing customer service interruptions in the service restoration process.

Hu, Rongxing↗

DOE OSTI2022

Disentangling long and short distances in momentum-space TMDs

The extraction of nonperturbative TMD physics is made challenging by prescriptions that shield the Landau pole, which entangle long- and short-distance contributions in momentum space. The use of different prescriptions then makes the comparison of fit results for underlying nonperturbative contributions not meaningful on their own. We propose a model-independent method to restrict momentum-space observables to the perturbative domain. This method is based on a set of integral functionals that act linearly on terms in the conventional position-space operator product expansion (OPE). Artifacts from the truncation of the integral can be systematically pushed to higher powers in Λ QCD /k T . We demonstrate that this method can be used to compute the cumulative integral of TMD PDFs over k T ≤ k$^{cut}_{T}$ in terms of collinear PDFs, accounting for both radiative corrections and evolution effects. This yields a systematic way of correcting the naive picture where the TMD PDF integrates to a collinear PDF, and for unpolarized quark distributions we find that when renormalization scales are chosen near k$^{cut}_{T}$, such corrections are a percent-level effect. We also show that, when supplemented with experimental data and improved perturbative inputs, our integral functionals will enable model-independent limits to be put on the non-perturbative OPE contributions to the Collins-Soper kernel and intrinsic TMD distributions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2025

CarbStor: Development, Analysis and Modification of Carbon Storing Model Soil Communities

Soil microbial communities carry out a number of key processes including plant growth promotion, bioremediation and cycling of nutrients. Carbon cycling is among the most important of these nutrients that are metabolized and processed by the soil microbial community. Many of the carbon inputs are converted to alternative organic forms of carbon that can be used by plants or act as biomass for microbial growth. However, inorganic forms of carbon can also be produced by soil microbial communities including calcium carbonate (CaCO 3 ). Production of calcium carbonate is beneficial for the ecosystem in several ways: it can stabilize soils and improve soil health, especially denser soils with high clay content, it can act as a method of bioremediation, it can serve as an alternative carbon source for plants and it can be a way to store carbon in soil in a stable, inorganic manner for the long term. While the chemistry surrounding individual species carrying out this process is well known what is lacking is an understanding of how species interact in a community to drive carbonate production. As all microbial species in soil exist in a community setting gaining this knowledge is critical to our predicting and controlling this microbial phenotype to greatly improve soil health. The CarbStor project is focused on developing, analyzing and modifying defined microbial soil consortia that express phenotypes at both the species and community level to convert carbon into recalcitrant stable sources such as precipitated carbonate or microbial necromass. To take full advantage of the soil community for this process we will need to fill several key knowledge gaps (KG), three of which are the focus of CarbStor. KG1: Whether and to what degree microbial communities can be developed that produce precipitated carbon via microbial metabolism. KG2: What interspecies interactions drive the individual member phenotypes in defined communities that lead to carbon precipitation. KG3: How can these interactions be modified to enhance carbon sequestration beyond what native communities are capable of. We hypothesize that in a carbon sequestering community only a subset of species will express phenotypes related to carbon storage processes. We also hypothesize that these phenotypes are expressed as a result of interactions with other species in the community that are not involved in carbon storage processes and that these interactions can be harnessed to enhance community carbon sequestration.

54 ENVIRONMENTAL SCIENCES↗

NASA NTRS2007

Spectral Retrieval of Latent Heating Profiles from TRMM PR data: Moistening Estimates over Tropical Ocean Regions - Part 3

The global hydrological cycle is central to the Earth's climate system, with rainfall and the physics of precipitation formation acting as the key links in the cycle. Two-thirds of global rainfall occurs in the tropics with the associated latent heating (LH) accounting for threefourths of the total heat energy available to the Earth's atmosphere. In the last decade, it has been established that standard products of LH from satellite measurements, particularly TRMM measurements, would be a valuable resource for scientific research and applications. Such products would enable new insights and investigations concerning the complexities of convection system life cycles, the diabatic heating controls and feedbacks related to rne-sosynoptic circulations and their forecasting, the relationship of tropical patterns of LH to the global circulation and climate, and strategies for improving cloud parameterizations In environmental prediction models. However, the LH and water vapor profile or budget (called the apparent moisture sink, or Q2) is closely related. This paper presented the development of an algorithm for retrieving Q2 using 'TRMM precipitation radar. Since there is no direct measurement of LH and Q2, the validation of algorithm usually applies a method called consistency check. Consistency checking involving Cloud Resolving Model (CRM)-generated LH and 42 profiles and algorithm-reconstructed is a useful step in evaluating the performance of a given algorithm. In this process, the CRM simulation of a time-dependent precipitation process (multiple-day time series) is used to obtain the required input parameters for a given algorithm. The algorithm is then used to "~econsti-LKt~h"e heating and moisture profiles that the CRM simulation originally produced, and finally both sets of conformal estimates (model and algorithm) are compared each other. The results indicate that discrepancies between the reconstructed and CM-simulated profiles for Q2, especially at low levels, are larger than those for latent heat. Larger discrepancies in Q2 at low levels are due to moistening for non-precipitating region that algorithm cannot reconstruct. Nevertheless, the algorithm-reconstructed total Q2 profiles are in good agreement with the CRM-simulated ones.

Shige, S.↗

DOE OSTI2022

A theoretical investigation of the hydrolysis of uranium hexafluoride: the initiation mechanism and vibrational spectroscopy

Depleted uranium hexafluoride (UF 6 ), a stockpiled byproduct of the nuclear fuel cycle, reacts readily with atmospheric humidity, but the mechanism is poorly understood. Here we compare several potential initiation steps at a consistent level of theory, generating underlying structures and vibrational modes using hybrid density functional theory (DFT) and computing relative energies of stationary points with double-hybrid (DH) DFT. A benchmark comparison is performed to assess the quality of DH-DFT data using reference energy differences obtained using a complete-basis-limit coupled-cluster (CC) composite method. The associated large-basis CC computations were enabled by a new general-purpose pseudopotential capability implemented as part of this work. Dispersion-corrected parameter-free DH-DFT methods, namely PBE0-DH-D3(BJ) and PBE-QIDH-D3(BJ), provided mean unsigned errors within chemical accuracy (1 kcal mol -1 ) for a set of barrier heights corresponding to the most energetically favorable initiation steps. The hydrolysis mechanism is found to proceed via intermolecular hydrogen transfer within van der Waals complexes involving UF 6 , UF 5 OH, and UOF 4 , in agreement with previous studies, followed by the formation of a previously unappreciated dihydroxide intermediate, UF 4 (OH) 2 . The dihydroxide is predicted to form under both kinetic and thermodynamic control, and, unlike the alternate pathway leading to the UO 2 F 2 monomer, its reaction energy is exothermic, in agreement with observation. Finally, harmonic and anharmonic vibrational simulations are performed to reinterpret literature infrared spectroscopy in light of this newly identified species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗