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Quantum interferences among Dexter energy transfer pathways

Dexter energy transfer in chemical systems moves an exciton (i.e., an electron–hole pair) from a donor chromophore to an acceptor chromophore through a bridge by a combination of bonded and non-bonded interactions. The transition is enabled by both one-electron/one-particle and two-electron/two-particle interaction mechanisms. Assuming that there is no real intermediate state population of an electron, hole, or exciton in the bridge, the transport involves two states that are coupled non-adiabatically. As such, coherent quantum interferences arise among the Dexter energy coupling pathways. These interferences, while related to well understood interferences in single-electron transfer, are much richer because of their two particle nature: the transfer of a triplet exciton involves the net transfer of both an electron and a hole. Despite this additional complexity, simple rules can govern Dexter coupling pathway interferences in special cases. As in the case of single-electron transfer, identical parallel coupling pathways can be constructively interfering and may enhance the Dexter transfer rate. Because of the virtual particle combinatorics associated with two-particle superexchange, two parallel Dexter coupling routes may be expected to enhance Dexter couplings by more than a factor of two. Here we explore Dexter coupling pathway interferences in non-covalent assemblies, employing a method that enables the assessment of Dexter coupling pathway strengths and interferences, in the context of one-particle and two-particle coupling interactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Rapid and Energy‐Efficient Synthesis of Disordered Rocksalt Cathodes

Abstract Lithium‐rich transition metal oxides with a cation‐disordered rocksalt structure (disordered rocksalt oxides or DRX) are promising candidates for sustainable, next‐generation Li‐ion cathodes due to their high energy densities and compositional flexibility, enabling Co‐ and Ni‐free battery chemistries. However, current methods to synthesize DRX compounds require either high temperature (≈1000 °C) sintering for several hours, or high energy ball milling for several days in an inert atmosphere. Both methods are time‐ and energy‐intensive, limiting the scale up of DRX production. The present study reports the rapid synthesis of various DRX compositions in ambient air via a microwave‐assisted solid‐state technique resulting in reaction times as short as 5 min, which are more than two orders of magnitude faster than current synthesis methods. The DRX compounds synthesized via microwave are phase‐pure and have a similar short‐ and long‐range structure as compared to DRX materials synthesized via a standard solid‐state route, resulting in nearly identical electrochemical performance. In some cases, microwave heating allows for better particle size and morphology control. Overall, the rapid and energy‐efficient microwave technique provides a more sustainable route to produce DRX materials, further incentivizes the development of next‐generation DRX cathodes, and is key to accelerating their optimization via high‐throughput studies.

25 ENERGY STORAGE↗

Symmetry restoration in mixed-spin paired heavy nuclei

The nature of the nuclear pairing condensates in heavy nuclei, specifically neutron-proton (spin-triplet), versus identical-particle (spin-singlet) pairing has been an active area of research for quite some time. In this work, we probe three candidates that should display spin-triplet, spin-singlet, and mixed-spin pairing. Using theoretical approaches such as the gradient method and symmetry-restoration techniques, we find the ground state of these nuclei in Hartree–Fock–Bogoliubov theory and compute ground state to ground state pair-transfer amplitudes to neighboring isotopes while simultaneously projecting to specific particle number and nuclear-spin values. We identify specific reactions for future experimental research that could shed light on spin-triplet and mixed-spin pairing.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Tank Closure Cesium Removal Project CST Simulant Cesium Batch Contact Kinetics Test Results and Column Performance Predictions

To evaluate the cesium removal capabilities of the caustic-washed R9120-B version of crystalline silicotitanate (CST) ion exchange media from Savannah River Site (SRS) waste during Tank Closure Cesium Removal (TCCR) column processing, batch contact kinetics tests were performed at 23 °C in SRS Average simulant. Cesium loading kinetics data was also collected (in current and previous testing; King, et al., 2018a) using the same simulant for an older CST sample (IE- 911) which was caustic-washed by the vendor many years ago and was recently retrieved from drums stored at SRS. (Note that R9120-B and IE-911 are believed to be identical materials, after the R9120-B was caustic washed by SRNL, and differ only by particle size and manufacturing date, and thus can be considered different batches). Although cesium loading kinetics testing can be conducted more rigorously using dynamic column tests, the batch contact method requires less simulant and considerably less experimental effort. Average percent removal data for batch contact samples for the two CST batches are provided in Table ES-1. Faster cesium uptake was observed with IE-911, although the loading rates for the two media batches were similar. After 5.5 hours of CST contact, 81% cesium removal was observed with R9120-B versus 86% removal with IE-911. Although these differences are small, the trend is consistent across the timed results, with the larger bead material always loading slower. These seemingly small differences in percent removal are believed to have a large impact on the column performance. Cesium loading curves for the two CST batches are provided in Figure ES-1 below. Faster cesium loading with IE-911 CST is presumed to be associated with the smaller average particle diameter (408 μm mean volume diameter) versus R9120-B (572 μm diameter). Cesium loading kinetic data was needed to conduct column performance comparisons (i.e., model predictions) for the two CST batches.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗

WE-H-BRA-08: A Monte Carlo Cell Nucleus Model for Assessing Cell Survival Probability Based On Particle Track Structure Analysis

Purpose: To correlate the damage produced by particles of different types and qualities to cell survival on the basis of nanodosimetric analysis and advanced DNA structures in the cell nucleus. Methods: A Monte Carlo code was developed to simulate subnuclear DNA chromatin fibers (CFs) of 30nm utilizing a mean-free-path approach common to radiation transport. The cell nucleus was modeled as a spherical region containing 6000 chromatin-dense domains (CDs) of 400nm diameter, with additional CFs modeled in a sparser interchromatin region. The Geant4-DNA code was utilized to produce a particle track database representing various particles at different energies and dose quantities. These tracks were used to stochastically position the DNA structures based on their mean free path to interaction with CFs. Excitation and ionization events intersecting CFs were analyzed using the DBSCAN clustering algorithm for assessment of the likelihood of producing DSBs. Simulated DSBs were then assessed based on their proximity to one another for a probability of inducing cell death. Results: Variations in energy deposition to chromatin fibers match expectations based on differences in particle track structure. The quality of damage to CFs based on different particle types indicate more severe damage by high-LET radiation than low-LET radiation of identical particles. In addition, the model indicates more severe damage by protons than of alpha particles of same LET, which is consistent with differences in their track structure. Cell survival curves have been produced showing the L-Q behavior of sparsely ionizing radiation. Conclusion: Initial results indicate the feasibility of producing cell survival curves based on the Monte Carlo cell nucleus method. Accurate correlation between simulated DNA damage to cell survival on the basis of nanodosimetric analysis can provide insight into the biological responses to various radiation types. Current efforts are directed at producing cell survival curves for high-LET radiation.

60 APPLIED LIFE SCIENCES↗

Unsupervised learning approaches to characterizing heterogeneous samples using X-ray single-particle imaging

One of the outstanding analytical problems in X-ray single-particle imaging (SPI) is the classification of structural heterogeneity, which is especially difficult given the low signal-to-noise ratios of individual patterns and the fact that even identical objects can yield patterns that vary greatly when orientation is taken into consideration. Proposed here are two methods which explicitly account for this orientation-induced variation and can robustly determine the structural landscape of a sample ensemble. The first, termed common-line principal component analysis (PCA), provides a rough classification which is essentially parameter free and can be run automatically on any SPI dataset. The second method, utilizing variation auto-encoders (VAEs), can generate 3D structures of the objects at any point in the structural landscape. Both these methods are implemented in combination with the noise-tolerant expand–maximize–compress (EMC) algorithm and its utility is demonstrated by applying it to an experimental dataset from gold nanoparticles with only a few thousand photons per pattern. Both discrete structural classes and continuous deformations are recovered. These developments diverge from previous approaches of extracting reproducible subsets of patterns from a dataset and open up the possibility of moving beyond the study of homogeneous sample sets to addressing open questions on topics such as nanocrystal growth and dynamics, as well as phase transitions which have not been externally triggered.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Open Specy 1.0: Automated (Hyper)spectroscopy for Microplastics

Microplastic spectral analysis is one of the most time-consuming processes in studying microplastic pollution, often requiring days per sample. Researchers are transitioning to automated batch and hyperspectral image analysis techniques to enhance efficiency. Open Specy, initially aimed at manual single-spectrum analysis, has now integrated automated methods. This updated version, Open Specy 1.0, introduces several new features, including two algorithms for automated processing (smoothing and particle compression), an extensive library containing over 40,000 open-source Raman and FTIR spectra, and two machine learning classifiers (logistic regression and k medoids) developed from this library. Furthermore, it includes a revamped user interface, an R package, and a benchmark data set for testing future advancements in automated techniques. Researchers evaluated various configurations for hyperspectral smoothing, particle identification, compression, and splitting, to achieve combined recovery rates between 50 and 150% particle counts, identities, and sizes with a coefficient of variation (CV) of less than 40% (the accredited standard). Mean absorbance times the standard deviation provided a consistent particle identification. Hyperspectral smoothing led to a 96% combined recovery rate and reduced variability (CV = 38%) compared to the 86% recovery (CV = 83%) of nonsmoothed controls. Additionally, compressing spectra for particles was significantly faster (>3x) and showed similar accuracy but with reduced variability than processing each pixel individually. Key challenges persist in automating spectral analysis, particularly in refining particle splitting algorithms, and improving identification routines to minimize false positives and negatives. In conclusion, new methods in sample preparation for better stabilization and dispersion of particles could overcome some of these issues.

13 HYDRO ENERGY↗

Communication: Distinguishing between short-time non-Fickian diffusion and long-time Fickian diffusion for a random walk on a crowded lattice

The motion of cells and molecules through biological environments is often hindered by the presence of other cells and molecules. A common approach to modeling this kind of hindered transport is to examine the mean squared displacement (MSD) of a motile tracer particle in a lattice-based stochastic random walk in which some lattice sites are occupied by obstacles. Unfortunately, stochastic models can be computationally expensive to analyze because we must average over a large ensemble of identically prepared realizations to obtain meaningful results. To overcome this limitation we describe an exact method for analyzing a lattice-based model of the motion of an agent moving through a crowded environment. Using our approach we calculate the exact MSD of the motile agent. Our analysis confirms the existence of a transition period where, at first, the MSD does not follow a power law with time. However, after a sufficiently long period of time, the MSD increases in proportion to time. This latter phase corresponds to Fickian diffusion with a reduced diffusivity owing to the presence of the obstacles. Our main result is to provide a mathematically motivated, reproducible, and objective estimate of the amount of time required for the transport to become Fickian. Our new method to calculate this crossover time does not rely on stochastic simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Are the U.S. Biorefineries Over the Hurdle of 2000 Ton Daily Throughput Yet?

The efficient utilization of lignocellulosic biomass for biofuel and biochemical production is hindered by material handling issues such as clogging and segregation among other challenges. Preprocessing methods such as drying, screening, and milling have improved conversion yield but have not sufficiently enhanced flowability, especially herbaceous biomass. The poor flowability of herbaceous biomass is rooted in some particle attributes that remain less altered by those methods, e.g., irregular particle shape, high roughness, and high compressibility, making it hard to scale up throughput to a key benchmark for a biorefinery – 2000 ton per day. Applying additional preprocessing methods like pelletization and torrefaction to drastically change those particle attributes can improve flow and handling but has not been comprehensively verified through test. The flowability of herbaceous biomass feedstock formats generated by three different preprocessing methods was recently assessed at Idaho National Laboratory’s Biomass Feedstock National User Facility: first, loose particles size reduced from as-received materials; second, pellets produced from an efficient densification process; and third, powders milled from torrefied pellets. Benchmarking tests including static angle of repose, basic flow energy measured in a powder rheometer, and discharge flow in an adjustable hopper, were conducted to evaluate those feedstock formats. Beyond the capacity of existing experimental apparatuses, a digital engineering approach involving flow simulations and AI models were used to identity the material attributes and processing parameters that have dominant influences on flow throughput. Techno-economic analysis focusing on hopper flow as a typical material handling operation was conducted for those feedstock formats. Perspectives will be discussed on whether the 2000-ton daily throughput for a biorefinery is achievable at an acceptable cost by using any of the tested preprocessing methods.

09 - BIOMASS FUELS↗

Spin relaxation rate for heavy quarks in weakly coupled QCD plasma

We compute the relaxation rate of the spin density of heavy quarks in a perturbative QCD plasma to leading-log order in the coupling constant g. The spin relaxation rate Γ s in spin hydrodynamics is shown to be Γ s ~ g 4 log(1/g)T(T/M) 2 in the heavy-quark limit T/M $\ll$ 1, which is smaller than the relaxation rate of other non- hydrodynamic modes by additional powers of T/M. We demonstrate three different methods to evaluate the spin relaxation rate: 1) the Green-Kubo formula in the spin hydrodynamic regime, 2) the spin density correlation function in the strict hydrodynamic limit, and 3) quantum kinetic theory of the spin distribution function in momentum space. We highlight the interesting differences between these methods, while they are ultimately connected to each other by the underlying Ward-Takahashi identity for the non-conserved spin density.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Cylindrical Magnetron Development for Nb3sn Deposition via Magnetron Sputtering

Due to its better superconducting properties (critical temperature Tc~ 18.3 K, superheating field Hsh~ 400 mT), Nb₃Sn is considered as a potential alternative to niobium (Tc~ 9.25 K, Hsh~ 200 mT) for superconducting radiofrequency (SRF) cavities for particle acceleration. Magnetron sputtering is an effective method to produce superconducting Nb₃Sn films. We deposited superconducting Nb₃Sn films on samples with magnetron sputtering using co-sputtering, sequential sputtering, and sputtering from a stoichiometric target. Nb₃Sn films produced by magnetron sputtering in our previous experiments have achieved DC superconducting critical temperature up to 17.93 K and RF superconducting transition at 17.2 K. A magnetron sputtering system with two identical cylindrical cathodes that can be used to sputter Nb₃Sn films on cavities has been designed and is under development now. We report on the design and the current progress on the development of the system.

43 PARTICLE ACCELERATORS↗

Additive manufacturing of platinum group element (PGE) reference materials with a silica matrix

The microanalytical community has an outstanding need for platinum group element (PGE) reference materials, particularly for trace element analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICPMS). National Institute of Standards and Technology (NIST) glasses contain Rh, Pd, and Pt, but lack Ru, Os, and Ir. Synthesis of silicate PGE standards has proven difficult due the tendency of PGEs to form metallic nuggets. Additive manufacturing methods were used to produce PGE standards with a silica matrix. Monodispersed submicron PGE-doped Stöber particles were used as feedstock materials for electrophoretic deposition (EPD). Two-cm-sized samples produced by EPD were subsequently densified by thermal processing. The homogeneity of PGEs was tested using LA-ICPMS and concentrations were measured by laser ablation and solution ICPMS. The PGE concentrations ranged from 0.5 to 3 μg/g. The inhomogeneity was at the 3% RSD level for Ru, Rh, Ir, and Os throughout and 5% for Pt and Pd in the interior of the samples. Based on LA-ICPMS analyses, the interiors of the two samples have near identical concentrations in PGEs. The samples fabricated in this study represent the most complete and homogeneous PGE standards produced with a silicate matrix. The ability to produce multiple samples with the same composition provides opportunities for validating methods, monitoring long-term reproducibility, and facilitating interlaboratory comparisons.

36 MATERIALS SCIENCE↗

One-particle many-body Green’s function theory: Algebraic recursive definitions, linked-diagram theorem, irreducible-diagram theorem, and general-order algorithms

A thorough analytical and numerical characterization of the whole perturbation series of one-particle many-body Green’s function (MBGF) theory is presented in a pedagogical manner. Three distinct but equivalent algebraic (first-quantized) recursive definitions of the perturbation series of the Green’s function are derived, which can be combined with the well-known recursion for the self-energy. Six general-order algorithms of MBGF are developed, each implementing one of the three recursions, the ΔMPn method (where n is the perturbation order) [S. Hirata et al., J. Chem. Theory Comput. 11, 1595 (2015)], the automatic generation and interpretation of diagrams, or the numerical differentiation of the exact Green’s function with a perturbation-scaled Hamiltonian. They all display the identical, nondivergent perturbation series except ΔMPn, which agrees with MBGF in the diagonal and frequency-independent approximations at 1 ≤ n ≤ 3 but converges at the full-configuration-interaction (FCI) limit at n=∞ (unless it diverges). Numerical data of the perturbation series are presented for Koopmans and non-Koopmans states to quantify the rate of convergence towards the FCI limit and the impact of the diagonal, frequency-independent, or ΔMPn approximation. The diagrammatic linkedness and thus size-consistency of the one-particle Green’s function and self-energy are demonstrated at any perturbation order on the basis of the algebraic recursions in an entirely time-independent (frequency-domain) framework. The trimming of external lines in a one-particle Green’s function to expose a self-energy diagram and the removal of reducible diagrams are also justified mathematically using the factorization theorem of Frantz and Mills. Equivalence of ΔMPn and MBGF in the diagonal and frequency-independent approximations at 1 ≤ n ≤ 3 is algebraically proven, also ascribing the differences at n = 4 to the so-called semi-reducible and linked-disconnected diagrams

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Critical properties of scalar field theory with Lorentz violation: Exact treatment of Lorentz-violating mechanism

In this work, we compute analytically the infrared divergences of massless O(N) self-interacting scalar field theories with Lorentz violation, which are exact in the Lorentz-violating K{sub μν} coefficients, for evaluating the corresponding next-to-leading order critical exponents. For that, we apply three distinct and independent field-theoretic renormalization group methods. We find that the outcomes for the critical exponents are the same in the three methods and, furthermore, are identical to their Lorentz invariant counterparts. We generalize the results for all loop levels by employing a general theorem arising from the exact procedure and give the corresponding physical interpretation.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

SU-F-T-258: Efficacy of Exit Fluence-Based Dose Calculation for Prostate Radiation Therapy

Purpose: To investigate the efficacy of exit-fluence-based dose computation for prostate radiotherapy by determining if it estimates true dose more accurately than the original planning dose. Methods: Virtual exit-fluencebased dose computation was performed for 19 patients, each with 9–12 repeat CT images. For each patient, a 78 Gy treatment plan was created utilizing 5 mm CTV-to-PTV and OAR-to-PRV margins. A Monte Carlo framework was used to compute dose and exit-fluence images for the planning image and for each repeat CT image based on boney-anatomyaligned and prostate-centroid-aligned CTs. Identical source particles were used for the MC dose-computations on the planning and repeat CTs to maximize correlation. The exit-fluence-based dose and image were computed by multiplying source particle weights by FC(x,y)=FP(x,y)/FT(x,y), where (x,y) are the source particle coordinates projected to the exit-fluence plane and we denote the dose/fluence from the plan by (DP,FP), from the repeat-CT as (DT,FT), and the exit-fluence computation by (DFC,FFC). DFC mimics exit-fluence backprojection through the planning image as FT=FFC. Dose estimates were intercompared to judge the efficacy of exit-fluence-based dose computation. Results: Boney- and prostate-centroid aligned results are combined as there is no statistical difference between them, yielding 420 dose comparisons per dose-volume metric. DFC is more accurate than DP for 46%, 33%, and 44% of cases in estimating CTV D98, D50, and D2 respectively. DFC improved rectum D50 and D2 estimates 54% and 49% respectively and bladder D50 and D2 47 and 49% respectively. While averaged over all patients and images DFC and DP were within 3.1% of DT, they differed from DT by as much as 22% for GTV D98, 71% for the Bladder D50, 17% for Bladder D2, 19% for Rectum D2. Conclusion: Exit-fluence based dose computations infrequently improve CTV or OAR dose estimates and should be used with caution. Research supported in part by Varian Medical Systems.

60 APPLIED LIFE SCIENCES↗

Lattice QCD Calculation of Nucleon Structure

It is emphasized in the 2015 NSAC Long Range Plan that "understanding the structure of hadrons in terms of QCD's quarks and gluons is one of the central goals of modern nuclear physics." Over the last three decades, lattice QCD has developed into a powerful tool for ab initio calculations of strong-interaction physics. Up until now, it is the only theoretical approach to solving QCD with controlled statistical and systematic errors. Since 1985, we have proposed and carried out first-principles calculations of nucleon structure and hadron spectroscopy using lattice QCD which entails both algorithmic development and large-scale computer simulation. We started out by calculating the nucleon form factors -- electromagnetic, axial-vector, πNN, and scalar form factors, the quark spin contribution to the proton spin, the strangeness magnetic moment, the quark orbital angular momentum, the quark momentum fraction, and the quark and glue decomposition of the proton momentum and angular momentum. The first round of calculations were done with Wilson fermions in the `quenched' approximation where the dynamical effects of the quarks in the sea are not taken into account in the Monte Carlo simulation to generate the background gauge configurations. Beginning in 2000, we have started implementing the overlap fermion formulation into the spectroscopy and structure calculations. This is mainly because the overlap fermion honors chiral symmetry as in the continuum. It is going to be more and more important to take the symmetry into account as the simulations move closer to the physical point where the u and d quark masses are as light as a few MeV only. We began with lattices which have quark masses in the sea corresponding to a pion mass at ~ 300 MeV and obtained the strange form factors, charm and strange quark masses, the charmonium spectrum and the D s meson decay constant f D s , the strangeness and charmness, the meson mass decomposition and the strange quark spin from the anomalous Ward identity. Recently, we have started to include multiple lattices with different lattice spacings and different volumes including large lattices at the physical pion mass point. We are getting quite close to being able to calculate the hadron structure at the physical point and to do the continuum and large volume extrapolations, which is our ultimate aim. We have now finished several projects which have included these systematic corrections. They include the leptonic decay width of the ρ, the πN sigma and strange sigma terms, and the strange quark magnetic moment. Over the years, we have also studied hadron spectroscopy with lattice calculations and in phenomenology. These include Roper resonance, pentaquark state, charmonium spectrum, glueballs, scalar mesons a 0 (1450) and σ(600) and other scalar mesons, and the 1 -+ meson. In addition, we have employed the canonical approach to explore the first-order phase transition and the critical point at finite density and finite temperature. We have also discovered a new parton degree of freedom -- the connected sea partons, from the path-integral formulation of the hadronic tensor, which explains the experimentally observed Gottfried sum rule violation. Combining experimental result on the strange parton distribution, the CT10 global fitting results of the total u and d anti-partons and the lattice result of the ratio of the momentum fraction of the strange vs that of u or d in the disconnected insertion, we have shown that the connected sea partons can be isolated. In this final technical report, we shall present a few representative highlights that have been achieved in the project.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Efficient Fourier basis particle simulation

The standard particle-in-cell algorithm suffers from grid heating. There exists a gridless alternative which bypasses the deposition step and calculates each Fourier mode of the charge density directly from the particle positions. We show that a gridless method can be computed efficiently through the use of an Unequally Spaced Fast Fourier Transform (USFFT) algorithm. After a spectral field solve, the forces on the particles are calculated via the inverse USFFT (a rapid solution of an approximate linear system). We provide one and two dimensional implementations of this algorithm with an asymptotic runtime of O ( N p + N m D log ⁡ N m D ) for each iteration, identical to the standard PIC algorithm (where N p is the number of particles, N m is the number of Fourier modes, and D is the spatial dimensionality of the problem). We demonstrate superior energy conservation and reduced noise, as well as convergence of the energy conservation at small time steps.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗