Results for “Structural error” — Page 84

DOE OSTI2022

Conservative Numerical Schemes with Optimal Dispersive Wave Relations: Part II. Numerical Evaluations

A new energy and enstrophy conserving scheme (EEC) for the shallow water equations is proposed and evaluated using a suite of test cases over the global spherical or bounded domain. The evaluation is organized around a set of pre-defined properties: accuracy of individual operators, accuracy of the whole scheme, conservation of key quantities, control of the divergence variable, representation of the energy and enstrophy spectra, and simulation of nonlinear dynamics. The results confirm that the scheme is between the first and second order accurate, and conserves the total energy and potential enstrophy up to the time truncation errors. Here, the scheme is capable of producing more physically realistic energy and enstrophy spectra, indicating that it can help prevent the unphysical energy cascade towards the finest resolvable scales. With an optimal representation of the dispersive wave relations, the scheme is able to keep the flow close to being non-divergent, and maintain the geostrophically balanced structures with large-scale geophysical flows over long-term simulations.

54 ENVIRONMENTAL SCIENCES↗

DOE OSTI2016

A quantitative model of application slow-down in multi-resource shared systems

Scheduling multiple jobs onto a platform enhances system utilization by sharing resources. The benefits from higher resource utilization include reduced cost to construct, operate, and maintain a system, which often include energy consumption. Maximizing these benefits comes at a price-resource contention among jobs increases job completion time. In this study, we analyze slow-downs of jobs due to contention for multiple resources in a system; referred to as dilation factor. We observe that multiple-resource contention creates non-linear dilation factors of jobs. From this observation, we establish a general quantitative model for dilation factors of jobs in multi-resource systems. A job is characterized by a vector-valued loading statistics and dilation factors of a job set are given by a quadratic function of their loading vectors. We demonstrate how to systematically characterize a job, maintain the data structure to calculate the dilation factor (loading matrix), and calculate the dilation factor of each job. We validate the accuracy of the model with multiple processes running on a native Linux server, virtualized servers, and with multiple MapReduce workloads co-scheduled in a cluster. Evaluation with measured data shows that the D-factor model has an error margin of less than 16%. We extended the D-factor model to capture the slow-down of applications when multiple identical resources exist such as multi-core environments and multi-disks environments. Finally, validation results of the extended D-factor model with HPC checkpoint applications on the parallel file systems show that D-factor accurately captures the slow down of concurrent applications in such environments.

97 MATHEMATICS AND COMPUTING↗

DOE OSTI2016

Continuous Fluorescence Assays for Reactions Involving Adenine

5'-Methylthioadenosine phosphorylase (MTAP) and 5'-methylthioadenosine nucleosidase (MTAN) catalyze the phosphorolysis and hydrolysis of 5'-methylthioadenosine (MTA), respectively. Both enzymes have low KM values for their substrates. Kinetic assays for these enzymes are challenging, as the ultraviolet absorbance spectra for reactant MTA and product adenine are similar. We report a new assay using 2-amino-5'-methylthioadenosine (2AMTA) as an alternative substrate for MTAP and MTAN enzymes. Hydrolysis or phosphorolysis of 2AMTA forms 2,6-diaminopurine, a fluorescent and easily quantitated product. We kinetically characterize 2AMTA with human MTAP, bacterial MTANs and use 2,6-diaminopurine as a fluorescent substrate for yeast adenine phosphoribosyltransferase. 2AMTA was used as the substrate to kinetically characterize the dissociation constants for three-transition-state analogue inhibitors of MTAP and MTAN. Kinetic values obtained from continuous fluorescent assays with MTA were in good agreement with previously measured literature values, but gave smaller experimental errors. Chemical synthesis from ribose and 2,6-dichloropurine provided crystalline 2AMTA as the oxalate salt. Chemo-enzymatic synthesis from ribose and 2,6-diaminopurine produced 2-amino-S-adenosylmethionine for hydrolytic conversion to 2AMTA. Interaction of 2AMTA with human MTAP was also characterized by pre-steady-state kinetics and by analysis of the crystal structure in a complex with sulfate as a catalytically inert analogue of phosphate. Furthermore, this assay is suitable for inhibitor screening by detection of fluorescent product, for quantitative analysis of hits by rapid and accurate measurement of inhibition constants in continuous assays, and pre-steady-state kinetic analysis of the target enzymes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2012

A digital optical phase-locked loop for diode lasers based on field programmable gate array

We have designed and implemented a highly digital optical phase-locked loop (OPLL) for diode lasers in atom interferometry. The three parts of controlling circuit in this OPLL, including phase and frequency detector (PFD), loop filter and proportional integral derivative (PID) controller, are implemented in a single field programmable gate array chip. A structure type compatible with the model MAX9382/MCH12140 is chosen for PFD and pipeline and parallelism technology have been adapted in PID controller. Especially, high speed clock and twisted ring counter have been integrated in the most crucial part, the loop filter. This OPLL has the narrow beat note line width below 1 Hz, residual mean-square phase error of 0.14 rad{sup 2} and transition time of 100 {mu}s under 10 MHz frequency step. A main innovation of this design is the completely digitalization of the whole controlling circuit in OPLL for diode lasers.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

DOE OSTI2016

Hadron structure from lattice QCD

Recent progress in lattice QCD calculations of nucleon structure will be presented. Calculations of nucleon matrix elements and form factors have long been difficult to reconcile with experiment, but with advances in both methodology and computing resources, this situation is improving. Some calculations have produced agreement with experiment for key observables such as the axial charge and electromagnetic form factors, and the improved understanding of systematic errors will help to increase confidence in predictions of unmeasured quantities. The long-omitted disconnected contributions are now seeing considerable attention and some recent calculations of them will be discussed.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

DOE OSTI2014

Verification of the astrometric performance of the Korean VLBI network, using comparative SFPR studies with the VLBA AT 14/7 mm

The Korean VLBI Network (KVN) is a new millimeter VLBI dedicated array with the capability to simultaneously observe at multiple frequencies, up to 129 GHz. The innovative multi-channel receivers present significant benefits for astrometric measurements in the frequency domain. The aim of this work is to verify the astrometric performance of the KVN using a comparative study with the VLBA, a well-established instrument. For that purpose, we carried out nearly contemporaneous observations with the KVN and the VLBA, at 14/7 mm, in 2013 April. The KVN observations consisted of simultaneous dual frequency observations, while the VLBA used fast frequency switching observations. We used the Source Frequency Phase Referencing technique for the observational and analysis strategy. We find that having simultaneous observations results in superior compensation for all atmospheric terms in the observables, in addition to offering other significant benefits for astrometric analysis. We have compared the KVN astrometry measurements to those from the VLBA. We find that the structure blending effects introduce dominant systematic astrometric shifts, and these need to be taken into account. We have tested multiple analytical routes to characterize the impact of the low-resolution effects for extended sources in the astrometric measurements. The results from the analysis of the KVN and full VLBA data sets agree within 2σ of the thermal error estimate. We interpret the discrepancy as arising from the different resolutions. We find that the KVN provides astrometric results with excellent agreement, within 1σ, when compared to a VLBA configuration that has a similar resolution. Therefore, this comparative study verifies the astrometric performance of the KVN using SFPR at 14/7 mm, and validates the KVN as an astrometric instrument.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2013

GAPS IN THE GD-1 STAR STREAM

GD-1 is a long, thin, Milky Way star stream that has readily visible density variations along its length. We quantify the locations, sizes, and statistical significance of the density structure, i.e., gaps, using a set of scaled filters. The shapes of the filters are based on the gaps that develop in simulations of dark matter sub-halos crossing a star stream. The high Galactic latitude 8.4 kpc long segment of GD-1 that we examine has 8 {+-} 3 gaps of 99% significance or greater, with the error estimated on the basis of tests of the gap-filtering technique. The cumulative distribution of gaps more than three times the width of the stream is in good agreement with predictions for dark matter sub-halo encounters with cold star streams. The number of gaps narrower than three times the width of the GD-1 stream falls well below the cold stream prediction which is taken into account for the gap creation rate integrated over all sizes. Simple warm stream simulations scaled to GD-1 show that the falloff in gaps is expected for sub-halos below a mass of 10{sup 6} M{sub Sun }. The GD-1 gaps requires 100 sub-halos >10{sup 6} M{sub Sun} within 30 kpc, the apocenter of GD-1 orbit. These results are consistent with LCDM sub-halo predictions but further improvements in stream signal-to-noise and gap modeling will be welcome.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

Data-driven modeling and control of an X-ray bimorph adaptive mirror

Adaptive X-ray mirrors are being adopted on high-coherent-flux synchrotron and X-ray free-electron laser beamlines where dynamic phase control and aberration compensation are necessary to preserve wavefront quality from source to sample, yet challenging to achieve. Additional difficulties arise from the inability to continuously probe the wavefront in this context, which demands methods of control that require little to no feedback. In this work, a data-driven approach to the control of adaptive X-ray optics with piezo-bimorph actuators is demonstrated. This approach approximates the non-linear system dynamics with a discrete-time model using random mirror shapes and interferometric measurements as training data. For mirrors of this type, prior states and voltage inputs affect the shape-change trajectory, and therefore must be included in the model. Without the need for assumed physical models of the mirror's behavior, the generality of the neural network structure accommodates drift, creep and hysteresis, and enables a control algorithm that achieves shape control and stability below 2 nm RMS. Using a prototype mirror and ex situ metrology, it is shown that the accuracy of our trained model enables open-loop shape control across a diverse set of states and that the control algorithm achieves shape error magnitudes that fall within diffraction-limited performance.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

DOE OSTI2023

Convex Q-Learning in Continuous Time with Application to Dispatch of Distributed Energy Resources

Convex Q-learning is a recent approach to reinforcement learning, motivated by the possibility of a firmer theory for convergence, and the possibility of making use of greater a priori knowledge regarding policy or value function structure. This paper explores algorithm design in the continuous time domain, with a finite-horizon optimal control objective. The main contributions are (i) The new Q-ODE: a model-free characterization of the Hamilton-Jacobi-Bellman equation. (ii) A formulation of Convex Q-learning that avoids approximations appearing in prior work. The Bellman error used in the algorithm is defined by filtered measurements, which is necessary in the presence of measurement noise. (iii) Convex Q-learning with linear function approximation is a convex program. It is shown that the constraint region is bounded, subject to an exploration condition on the training input. (iv) The theory is illustrated in application to resource allocation for distributed energy resources, for which the theory is ideally suited.

Lu, Fan↗

DOE OSTI2016

TU-H-CAMPUS-JeP2-04: Deriving Delivered Doses to Assess the Viability of 2.5 Mm Margins in Head and Neck SBRT

Purpose: To calculate the delivered dose for head and neck SBRT patients using pre-treatment images. This delivered dose was then used to determine the viability of 2.5 mm margins. Methods: Daily cone beam CTs (CBCTs) were collected for 20 patients along with a planning CT, planned dose, and planning structures. The day 1 CBCT was aligned to the planning CT using the treatment shifts (six degrees of freedom) and then the dose and contours were transferred to the CBCT. The day 1 CBCT becomes the reference image for days 2–5. The day 2–5 CBCTs were also aligned to the planning CT using the treatment shifts given and the dose transferred. The day 2–5 CBCTs were then deformably registered to the day 1 CBCT. The doses delivered on days 2–5 were then deformed to the day 1 CBCT where they could be accumulated. This was achieved with MIM 6.5.1 (MIM Software, Cleveland OH). The accumulated doses for the 20 patients were evaluated against the planned doses using the initial planning criteria as points of comparison. Results: The delivered CTV dose conformed to the planned 98.6% coverage, with an average decrease of 2.6% between planned and delivered coverage. This implies the 2.5 mm margin was sufficient. Larger CTVs correlated to smaller differences between planned and delivered coverage. Delivered dose to critical structures including the spinal cord, mandible, brain, brainstem, and larynx was acceptable, with differences between planned and delivered max dose <5% on average. Similarly for the parotid glands, globes, cochlear, optic nerve, lens, and submandibular glands, differences between planned and delivered doses were generally <5%. Conclusion: The 2.5 mm margin provided acceptable CTV coverage, adequately accounting for setup errors. Organ at risk sparing was also satisfactory. Small tumor volumes (<20 cc) may require a larger margin to treat effectively.

60 APPLIED LIFE SCIENCES↗

DOE OSTI2021

AI to Predict Glass Compositions Satisfying Property and Cooling Rate Criteria

This project aimed to develop a predictive, artificial intelligence/machine learning-based model to identify glass compositions satisfying specified property requirements. Such a model would provide a systematic approach for narrowing down the nearly infinite range of possible compositions for glasses and minimize unnecessary experimental trial and error. A large empirical data set for training and testing the algorithm was obtained from the SciGlass database. It contains glass compositions and corresponding property data from a wide range of literature sources. However, the currently available form of this data, recently released under an open database license, is not conducive to easy querying and use. The data structure was deciphered and a customized parsing code developed to make this data more usable for the current and future work. Neural network models were developed and trained on viscosity data from the database and demonstrated potential for improving prediction accuracy over a traditional regression model.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

DOE OSTI2017

Magellan/M2FS Spectroscopy of Galaxy Clusters: Stellar Population Model and Application to Abell 267

We report the results of a pilot program to use the Magellan/M2FS spectrograph to survey the galactic populations and internal kinematics of galaxy clusters. For this initial study, we present spectroscopic measurements for 223 quiescent galaxies observed along the line of sight of the galaxy cluster Abell 267 (z∼0.23). We develop a Bayesian method for modeling the integrated light from each galaxy as a simple stellar population, with free parameters that specify the redshift (v{sub los}/c) and characteristic age, metallicity ([Fe/H]), alpha-abundance ([α/Fe]), and internal velocity dispersion (σ{sub int}) for individual galaxies. Parameter estimates derived from our 1.5 hr observation of A267 have median random errors of σ{sub v{sub l{sub o{sub s}}}}=20 km s{sup −1}, σ{sub Age}=1.2 Gyr, σ{sub [Fe/H]}=0.11 dex, σ{sub [α/Fe]}=0.07 dex, and σ{sub σ{sub i{sub n{sub t}}}}=20 km s{sup −1}. In a companion paper, we use these results to model the structure and internal kinematics of A267.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2012

D-Factor: A Quantitative Model of Application Slow-Down in Multi-Resource Shared Systems

Scheduling multiple jobs onto a platform enhances system utilization by sharing resources. The benefits from higher resource utilization include reduced cost to construct, operate, and maintain a system, which often include energy consumption. Maximizing these benefits comes at a price - resource contention among jobs increases job completion time. In this paper, we analyze slow-downs of jobs due to contention for multiple resources in a system; referred to as dilation factor. We observe that multiple-resource contention creates non-linear dilation factors of jobs. From this observation, we establish a general quantitative model for dilation factors of jobs in multi-resource systems. A job is characterized by a vector-valued loading statistics and dilation factors of a job set are given by a quadratic function of their loading vectors. We demonstrate how to systematically characterize a job, maintain the data structure to calculate the dilation factor (loading matrix), and calculate the dilation factor of each job. We validate the accuracy of the model with multiple processes running on a native Linux server, virtualized servers, and with multiple MapReduce workloads co-scheduled in a cluster. Evaluation with measured data shows that the D-factor model has an error margin of less than 16%. We also show that the model can be integrated with an existing on-line scheduler to minimize the makespan of workloads.

99 GENERAL AND MISCELLANEOUS↗

DOE OSTI2023

AGR-5/6/7 Thermal Model with Non-uniform Gas Gaps

Fuel compact temperatures are a crucial factor in assessing the irradiation performance of tri-structural isotropic fuel particles. In the absence of direct measurement, fuel compact temperatures were calculated using a three-dimensional finite element thermal model, which is subject to simulation uncertainty. The most dominant factor in the uncertainty of calculated fuel temperatures is the gas gap uncertainty due to the nub-to-shell clearance caused by a design error of AGR-5/6/7 capsules. The thermal model was revised to examine the most probable graphite offset position for six different days during the irradiation for Capsules 1 and 2. The analysis varied the offset distance and azimuthal direction at both the top and bottom of the holder. The best-fit offset was estimated based on the minimum root mean square error of the residuals (measured minus calculated) for the operational thermocouples (TCs). From these results, the following conclusions were made: (1) The holder offsets led to slightly lower average temperatures but wider temperature variations (lower minimum and higher peak fuel temperatures) for both Capsule 1 and Capsule 2. (2) During earlier cycles (162A–164B), when numerous TCs were still operational, the best-fit offset distance varied over a specific range for both the top and bottom ([0.002–0.0035 in.] for Capsule 1 and [0.003-0.004 in] for Capsule 2). In contrast, the offset azimuthal direction varied widely, especially for the offset at the bottom of the Capsule 1 holder. This is because holder movement was somewhat constrained at the top of Capsule 1 by the TC leads running through the capsule head and into the holder and by the through tubes in Capsule 2, but the Capsule 1 bottom did not have this type of constraint. (3) During later cycles, when all TCs failed, applying the maximum possible offset of 0.006 in. to the northwest direction for both the top and bottom resulted in a calculated peak fuel temperature of 1557? in Capsule 1 (i.e., a 135? increase from 1422? with zero offset on September 20, 2019 (166A)); the maximum offset of 0.0068 in. to the south for both top and bottom resulted in a calculated peak fuel temperature of 1110°C in Capsule 2 on April 20, 2020 (i.e., a 116? increase from 994? with zero offset (168A)). High peak fuel temperatures in Capsule 1 during Cycle 166A could be the cause of massive particle failure near the end of this cycle. (4) Even though the highest temperature at the tip of Type-N TCs, such as TC-1-7, slightly exceeded 1000?, the temperature along the TC wire reached as high as 1335? assuming an offset of 0.006 in. in the northwest of Capsule 1 holder near the end of Cycle 166A. This temperature significantly exceeds the temperature threshold at which TC degradation is expected to occur, ultimately contributing to considerable particle failures in Capsule 1. For eight Type-N TCs in Capsule 2, the peak TC line temperature was much lower (i.e., 1029°C for TC-2-5), assuming maximum offset of 00068 in. to the south during cycle 168A.

advanced gas reactors↗

DOE OSTI2023

AGR-5/6/7 Thermal Model with Non-uniform Gas Gaps

Fuel compact temperatures are a crucial factor in assessing the irradiation performance of tri-structural isotropic fuel particles. In the absence of direct measurement, fuel compact temperatures were calculated using a three-dimensional finite element thermal model, which is subject to simulation uncertainty. The most dominant factor in the uncertainty of calculated fuel temperatures is the gas gap uncertainty due to the nub-to-shell clearance caused by a design error of AGR-5/6/7 capsules. The thermal model was revised to examine the most probable graphite offset position for six different days during the irradiation for Capsules 1 and 2. The analysis varied the offset distance and azimuthal direction at both the top and bottom of the holder. The best-fit offset was estimated based on the minimum root mean square error of the residuals (measured minus calculated) for the operational thermocouples (TCs). From these results, the following conclusions were made: (1) The holder offsets led to slightly lower average temperatures but wider temperature variations (lower minimum and higher peak fuel temperatures) for both Capsule 1 and Capsule 2. (2) During earlier cycles (162A–164B), when numerous TCs were still operational, the best-fit offset distance varied over a specific range for both the top and bottom ([0.002–0.0035 in.] for Capsule 1 and [0.003-0.004 in] for Capsule 2). In contrast, the offset azimuthal direction varied widely, especially for the offset at the bottom of the Capsule 1 holder. This is because holder movement was somewhat constrained at the top of Capsule 1 by the TC leads running through the capsule head and into the holder and by the through tubes in Capsule 2, but the Capsule 1 bottom did not have this type of constraint. (3) During later cycles, when all TCs failed, applying the maximum possible offset of 0.006 in. to the northwest direction for both the top and bottom resulted in a calculated peak fuel temperature of 1557? in Capsule 1 (i.e., a 135? increase from 1422? with zero offset on September 20, 2019 (166A)); the maximum offset of 0.0068 in. to the south for both top and bottom resulted in a calculated peak fuel temperature of 1110°C in Capsule 2 on April 20, 2020 (i.e., a 116? increase from 994? with zero offset (168A)). High peak fuel temperatures in Capsule 1 during Cycle 166A could be the cause of massive particle failure near the end of this cycle. (4) Even though the highest temperature at the tip of Type-N TCs, such as TC-1-7, slightly exceeded 1000?, the temperature along the TC wire reached as high as 1335? assuming an offset of 0.006 in. in the northwest of Capsule 1 holder near the end of Cycle 166A. This temperature significantly exceeds the temperature threshold at which TC degradation is expected to occur, ultimately contributing to considerable particle failures in Capsule 1. For eight Type-N TCs in Capsule 2, the peak TC line temperature was much lower (i.e., 1029°C for TC-2-5), assuming maximum offset of 00068 in. to the south during cycle 168A.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2025

AGR-5/6/7 Thermal Model with Non-uniform Gas Gaps

Fuel compact temperatures are a crucial factor in assessing the irradiation performance of tri-structural isotropic fuel particles. In the absence of direct measurement, fuel compact temperatures were calculated using a three-dimensional finite element thermal model, which is subject to simulation uncertainty. The most dominant factor in the uncertainty of calculated fuel temperatures is the gas gap uncertainty due to the nub-to-shell clearance caused by a design error of AGR-5/6/7 capsules. The thermal model was revised to examine the most probable graphite offset position for six different days during the irradiation for Capsules 1 and 2. The analysis varied the offset distance and azimuthal direction at both the top and bottom of the holder. The best-fit offset was estimated based on the minimum root mean square error of the residuals (measured minus calculated) for the operational thermocouples (TCs). From these results, the following conclusions were made: (1) The holder offsets led to slightly lower average temperatures but wider temperature variations (lower minimum and higher peak fuel temperatures) for both Capsule 1 and Capsule 2. (2) During earlier cycles (162A–164B), when numerous TCs were still operational, the best-fit offset distance varied over a specific range for both the top and bottom ([0.002–0.0035 in.] for Capsule 1 and [0.003-0.004 in] for Capsule 2). In contrast, the offset azimuthal direction varied widely, especially for the offset at the bottom of the Capsule 1 holder. This is because holder movement was somewhat constrained at the top of Capsule 1 by the TC leads running through the capsule head and into the holder and by the through tubes in Capsule 2, but the Capsule 1 bottom did not have this type of constraint. (3) During later cycles, when all TCs failed, applying the maximum possible offset of 0.006 in. to the northwest direction for both the top and bottom resulted in a calculated peak fuel temperature of 1557? in Capsule 1 (i.e., a 135? increase from 1422? with zero offset on September 20, 2019 (166A)); the maximum offset of 0.0068 in. to the south for both top and bottom resulted in a calculated peak fuel temperature of 1110°C in Capsule 2 on April 20, 2020 (i.e., a 116? increase from 994? with zero offset (168A)). High peak fuel temperatures in Capsule 1 during Cycle 166A could be the cause of massive particle failure near the end of this cycle. (4) Even though the highest temperature at the tip of Type-N TCs, such as TC-1-7, slightly exceeded 1000?, the temperature along the TC wire reached as high as 1335? assuming an offset of 0.006 in. in the northwest of Capsule 1 holder near the end of Cycle 166A. This temperature significantly exceeds the temperature threshold at which TC degradation is expected to occur, ultimately contributing to considerable particle failures in Capsule 1. For eight Type-N TCs in Capsule 2, the peak TC line temperature was much lower (i.e., 1029°C for TC-2-5), assuming maximum offset of 00068 in. to the south during cycle 168A.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

DOE OSTI2026

Two-stage formation-energy correction (NbZr, TaZr, VZr)

This bundle contains the scripts, the raw and corrected per-structure data, and the manuscript plots for the NbZr / TaZr / VZr BCC binary formation energies and the associated RMSDs. Why a two-stage correction is necessary: The "raw" formation energy of every relaxed VASP configuration is computed in the usual way, FE_raw(c) = E_alloy(c) - sum_i x_i * E_pure_i , where E_pure_i are the per-atom total energies of the pure-element reference structures (Nb, Ta, V, Zr in the same BCC supercell, with identical INCAR / KPOINTS / PAW choices). With perfectly consistent reference runs the raw FE should vanish at the two pure-element endpoints (x = 0 and x = 1) by construction. In practice this does not hold for two reasons that are present in our dataset: 1. Reference-energy inconsistency (composition-dependent bias). Even with identical input parameters, the pure-element runs (stored in `corrected_DFT_pure_element_runs/`) differ slightly from the values that would be implied by the alloy runs at near-pure compositions (a few meV/atom). This bias is approximately linear in concentration, because the residual error in E_pure_Nb (or E_pure_Ta / E_pure_V) propagates into FE_raw(c) as (1 - x) * dE_pure_1, and the corresponding error in E_pure_Zr propagates as x * dE_pure_2. Left uncorrected, this produces a non-physical "tilt" of FE_raw(x) and shifts the entire FE-vs-x cloud away from zero at the endpoints. 2. Endpoint anchoring against the audited true endpoints. The strict endpoint values (FE_x0_meVatom, FE_x1_meVatom in `corrected_fe_strict_endpoints_20260518/strict_endpoint_check_20260518.csv`) were re-derived from an independent cross-check of the pure-element runs. After stage 1 removes the linear bias, the near-pure compositions in the alloy dataset still extrapolate to values that differ slightly from these audited endpoints — because stage 1 is fit from a few near-end alloy bins, not from the audited pure-element references themselves. The README.txt file discusses how these issues are addressed by the two-stage correction, and describes folder layout, pipeline summary, and how to re-run.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Ligand Many-Body Expansion as a General Approach for Accelerating Transition Metal Complex Discovery

Methods that accelerate the evaluation of molecular properties are essential for chemical discovery. While some degree of ligand additivity has been established for transition metal complexes, it is underutilized in asymmetric complexes, such as the square pyramidal coordination geometries highly relevant to catalysis. To develop predictive methods beyond simple additivity, we apply a many-body expansion to octahedral and square pyramidal complexes and introduce a correction based on adjacent ligands (i.e., the cis interaction model). We first test the cis interaction model on adiabatic spin-splitting energies of octahedral Fe(II) complexes, predicting DFT-calculated values of unseen binary complexes to within an average of 1.4 kcal/mol. Uncertainty analysis reveals the optimal basis, comprising the homoleptic and mer symmetric complexes. We next show that the cis model (i.e., the cis interaction model solved for the optimal basis) infers both DFT- and CCSD(T)-calculated model catalytic reaction energies to within 1 kcal/mol on average. The cis model predicts low-symmetry complexes with reaction energies outside the range of binary complex reaction energies. We observe that trans interactions are unnecessary for most monodentate systems but can be important for some combinations of ligands, such as complexes containing a mixture of bidentate and monodentate ligands. Lastly, we demonstrate that the cis model may be combined with Δ-learning to predict CCSD(T) reaction energies from exhaustively calculated DFT reaction energies and the same fraction of CCSD(T) reaction energies needed for the cis model, achieving around 30% of the error from using the CCSD(T) reaction energies in the cis model alone.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗