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At least 1,711 records · Page 95

Trapping and diffusion of fission products in ThO2 and CeO2

The trapping and diffusion of Br, Rb, Cs and Xe in ThO2 and CeO2 have been studied using an Ab Initio total energy method in the local-density approximation of density functional theory. Fission products incorporated in cation mono-vacancy, cation–anion di-vacancy and Schottky defect sites are found to be stable, with the cation mono-vacancy being the preferred site in most cases. In both oxides, Rb and Cs are the most likely to be trapped, and Xe is more difficult to incorporate than other fission products. The energy barriers for migration of each species in ThO2 and CeO2 are also calculated. Alkali metals are relatively more mobile than other fission products, and bromine is the least mobile.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

First-principles studies of Ni-Ta intermetallic compounds

The structural properties, heats of formation, elastic properties, and electronic structures of Ni-Ta intermetallic compounds are investigated in detail based on density functional theory. Our results indicate that all Ni-Ta intermetallic compounds calculated here are mechanically stable except for P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2}. Furthermore, we found that Pmmn-Ni{sub 3}Ta is the ground state stable phase of Ni{sub 3}Ta polymorphs. The polycrystalline elastic modulus has been deduced by using the Voigt-Reuss-Hill approximation. All Ni-Ta intermetallic compounds in our study, except for NiTa, are ductile materials by corresponding G/K values and poisson's ratio. The calculated heats of formation demonstrated that Ni{sub 2}Ta are thermodynamically unstable. Our results also indicated that all Ni-Ta intermetallic compounds analyzed here are conductors. The density of state demonstrated the structure stability increases with the Ta concentration. - Graphical abstract: Mechanical properties and formation heats of Ni-Ta intermetallic compounds are discussed in detail in this paper. Highlights: Black-Right-Pointing-Pointer Ni-Ta intermetallic compounds are investigated by first principle calculations. Black-Right-Pointing-Pointer P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2} are mechanically unstable phases. Black-Right-Pointing-Pointer Pmmn-Ni{sub 3}Ta is ground stable phase of Ni{sub 3}Ta polymorphs. Black-Right-Pointing-Pointer All Ni-Ta intermetallic compounds are conducting materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ab initio density functional theory investigation of the structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases

A density functional theory study of structural, electronical and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. In the exchange–correlation potential, generalized gradient approximation (PBE-GGA) has been used to calculate lattice parameters, bulk modulus, cohesive energy, dielectric function and energy loss spectra. The electronic band structure of this compound has been calculated using the above two approximations as well as another form of PBE-GGA, proposed by Engle and Vosko (EV-GGA). It is found that the hexagonal phase of Ca{sub 3}Sb{sub 2} has an indirect gap in the Γ→N direction; while in the cubic phase there is a direct-gap at the Γ point in the PBE-GGA and EV-GGA. Effects of applying pressure on the band structure of the system studied and optical properties of these systems were calculated. - Graphical abstract: A density functional theory study of structural, electronic and optical properties of Ca{sub 3}Sb{sub 2} compound in hexagonal and cubic phases is presented. Display Omitted - Highlights: • Physical properties of Ca{sub 3}Sb{sub 2} in hexagonal and cubic phases are investigated. • It is found that the hexagonal phase is an indirect gap semiconductor. • Ca{sub 3}Sb{sub 2} is a direct-gap semiconductor at the Γ point in the cubic phase. • By increasing pressure the semiconducting band gap and anti-symmetry gap are decreased.

36 MATERIALS SCIENCE↗

Uncertainty guided online ensemble for non-stationary data streams in fusion science

Machine Learning (ML) is poised to play a pivotal role in the development and operation of next-generation fusion devices. Fusion data shows non-stationary behavior with distribution drifts, resulted by both experimental evolution and machine wear-and-tear. ML models assume stationary distribution and fail to maintain performance when encountered with such non-stationary data streams. Online learning techniques have been leveraged in other domains, however it has been largely unexplored for fusion applications. In this paper, we investigate online learning for continuous adaptation to drifting data streams in the prediction of Toroidal Field (TF) coils deflection at the DIII-D fusion facility. We further address the short-term performance degradation inherent to standard online learning, which arises because ground truth is unavailable at prediction time. To mitigate this issue, we propose an uncertainty-guided online ensemble framework. The method leverages the Deep Gaussian Process Approximation (DGPA) for calibrated uncertainty estimation and uses these uncertainty measures to guide a meta-algorithm that aggregates predictions from learners trained over different historical horizons. Our results show that online learning reduces prediction error by 80% compared to a static model. The online ensemble and the proposed uncertainty-guided ensemble further reduce error by approximately 6%, and 10% respectively, relative to standard single-model online learning, while also providing calibrated uncertainty estimates to support operational decision-making.

AI↗

252 Cf yield calibration method for nuclear material accountancy and safeguards practitioners

Californium-252 is an isotope commonly encapsulated as a physically small but strong spontaneous fission neutron source for applications in industry, academia, and research. Within the nuclear safeguards community, a well-characterized 252 Cf source is often used as an accessible alternative for plutonium in calibrations measurements, which require the absolute source strength. Current methods of source strength quantification can provide an accurate estimate, approximately 1% uncertainty under optimal conditions, but are typically costly and time consuming. An alternative method was developed to determine 252 Cf source strength using passive neutron correlation counting (PNCC). The PNCC method enables institutions and facilities to perform 252 Cf source calibration measurements in-house using detection systems that are common within the nuclear safeguards community. This novel method was previously successfully demonstrated using neutron multiplicity well counters. However, the previous evaluation utilized detection systems with high neutron detection efficiencies, greater than 60%. The purpose of the current study is to extend the previous evaluation and demonstrate the feasibility of the PNCC 252 Cf calibration method for suite of coincidence counters with lower neutron detection efficiencies, between 15% and 35%, which are more commonly encountered in the field, as well as to provide a step-by-step guide to using the method. The neutron source used in this evaluation was previously certified by the National Institutes of Science and Technology (NIST), which provides a reference for the accuracy of the PNCC method. In conclusion, the present source yield calculations demonstrate excellent agreement with a NIST calibration technique and achieve a standard uncertainty below the target 1%.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The impact of urban configuration types on urban heat islands, air pollution, CO 2 emissions, and mortality in Europe: a data science approach

The world is becoming increasingly urbanized. As cities around the world continue to grow, it is important for urban planners and policymakers to understand how different urban configuration patterns affect the environment and human health. We aimed at identifying European urban configuration types, based on the Local Climate Zones categories and street design variables from Open Street Map, and evaluating their association with motorized traffic flows, Surface Urban Heat Island (SUHI) intensities, tropospheric nitrogen dioxide (NO 2 ), CO 2 per capita emissions and age-standardized mortality. We considered 946 European cities from 31 countries for the analysis defined in the 2018 Urban Audit database, of which 919 European cities were analysed. Data were collected at a 250 m × 250 m grid cell resolution. We divided all cities into five concentric rings based on the Burgess concentric urban planning model and calculated the mean values of all variables for each ring. First, to identify distinct urban configuration types, we applied the Uniform Manifold Approximation and Projection for Dimension Reduction method, followed by the k-means clustering algorithm. Next, statistical differences in exposures (including SUHI) and mortality between the resulting urban configuration types were evaluated using a Kruskal–Wallis test followed by a post-hoc Dunn's test. We identified four distinct urban configuration types characterising European cities: compact high density (n=246), open low-rise medium density (n=245), open low-rise low density (n=261), and green low density (n=167). Compact high density cities were a small size, had high population densities, and a low availability of natural areas. In contrast, green low-density cities were a large size, had low population densities, and a high availability of natural areas and cycleways. The open low-rise medium and low-density cities were a small to medium size with medium to low population densities and low to moderate availability of green areas. Motorised traffic flows and NO 2 exposure were significantly higher in compact high density and open low rise medium density cities when compared with green low density and open low-rise low density cities. Additionally, green low-density cities had a significantly lower SUHI effect compared with all other urban configuration types. Per person CO 2 emissions were significantly lower in compact high density cities compared with green low density cities. Lastly, green low density cities had significantly lower mortality rates when compared with all other urban configuration types. Our findings indicate that, although the compact city model is more sustainable, European compact cities still face challenges related to poor environmental quality and health. Our results have notable implications for urban and transport planning policies in Europe and contribute to the ongoing discussion on which city models can bring the greatest benefits for the environment, climate, and health.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Microwave-Assisted Synthesis of Silver Vanadium Phosphorus Oxide, Ag 2 VO 2 PO 4 : Crystallite Size Control and Impact on Electrochemistry

We study silver vanadium phosphorus oxide, Ag 2 VO 2 PO 4 , that is a promising cathode material for Li batteries due in part to its large capacity and high current capability. Herein, a new synthesis of Ag 2 VO 2 PO 4 based on microwave heating is presented, where the reaction time is reduced by approximately 100× relative to other reported methods, and the crystallite size is controlled via synthesis temperature, showing a linear correlation of crystallite size with temperature. Notably, under galvanostatic reduction, the Ag 2 VO 2 PO 4 sample with the smallest crystallite size delivers the highest capacity and shows the highest loaded voltage. Further, pulse discharge tests show a significant resistance decrease during the initial discharge coincident with the formation of Ag metal. Thus, the magnitude of the resistance decrease observed during pulse tests depends on the Ag 2 VO 2 PO 4 crystallite size, with the largest resistance decrease observed for the smallest crystallite size. Additional electrochemical measurements indicate a quasi-reversible redox reaction involving Li + insertion/deinsertion, with capacity fade due to structural changes associated with the discharge/charge process. In summary, this work demonstrates a faster synthetic approach for bimetallic polyanionic materials which also provides the opportunity for tuning of electrochemical properties through control of material physical properties such as crystallite size.

25 ENERGY STORAGE↗

SCF Framework, HF Stability, and RPA Correlation for Jordan–Wigner-Transformed Spin Hamiltonians on Arbitrary Coupling Topologies

Mapping spins to fermions via the Jordan–Wigner (JW) transformation can render mean-field (Hartree–Fock, HF) descriptions effective for strongly correlated spin systems. As established in recent work, the application of such approaches is not limited by the nonlocal structure of JW strings or by site ordering because string operators can be absorbed into Thouless rotations of a Slater determinant, and the variational optimization of a unitary Lie-algebraic similarity transformation removes any ordering dependence. Leveraging these ideas, we develop a self-consistent field (SCF) scheme that expresses the mean-field energy as a functional of the single-particle density matrix, providing an alternative to gradient-based optimization of Thouless parameters. We derive the analytical orbital Hessian to diagnose HF stability and compute the ground-state correlation energy through the random-phase approximation (RPA). Benchmark results for the XXZ and J 1 –J 2 model on one- and two-dimensional lattices demonstrate that RPA significantly improves mean-field accuracy.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Domain Separated Density Functional Theory for Reaction Energy Barriers and Optical Excitations

We recently proposed Domain Separated Density Functional Theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. Here, this work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: i), the screened-density approximation (SDA), and, ii), linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Pareto Optimization of Oligomer Polarizability and Dipole Moment Using a Genetic Algorithm

High-performance electronic components are highly sought after in order to produce increasingly smaller and cheaper electronic devices. Drawing inspiration from inorganic dielectric materials, in which both polarizability and polarization contribute, organic materials can also maximize both. For a large set of small molecules drawn from PubChem, a Pareto-like front appears between the polarizability and dipole moment, indicating the presence of an apparent trade-off between these two properties. We tested this balance in π-conjugated materials by searching for novel conjugated hexamers with simultaneously large polar- izabilities and dipole moments with potential use for dielectric materials. Using a genetic algorithm (GA) screening technique in conjunction with an approximate density functional tight-binding method for property calculations, we were able to efficiently search chemical space for optimal hexamers. Given the scope of chemical space, using the GA technique saves considerable time and resources by speeding up molecular searches compared to a systematic search. Here, we also explored the underlying structure–function relationships, including sequence and monomer properties, that characterize large polarizability and dipole moment regimes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Current-Induced Forces for Nonadiabatic Molecular Dynamics

We present general first-principles derivation of the expression for current-induced forces. The expression is applicable in nonequilibrium molecular systems with arbitrary intramolecular interactions and for any electron-nuclei coupling. It provides a controlled consistent way to account for quantum effects of nuclear motion around a classical trajectory, accounts for electronic non-Markov character of the friction tensor, and suggests a method for treatment beyond strictly adiabatic approximation. Lastly, we show the connection of the expression with previous studies and discuss effective ways to evaluate the friction tensor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Size-Dependent Coherent-Phonon Plasmon Modulation and Deformation Characterization in Gold Bipyramids and Nanojavelins

Localized surface plasmon resonances (LSPRs) arising from metallic nanoparticles offer an array of prospective applications that range from chemical sensing to biotherapies. Bipyramidal particles exhibit particularly narrow ensemble LSPR resonances that reflect small dispersity of size and shape but until recently were only synthetically accessible over a limited range of sizes with corresponding aspect ratios. Narrow size dispersion offers the opportunity to examine ensemble dynamical phenomena such as coherent phonons that induce periodic oscillations of the LSPR energy. Here, we characterize transient optical behavior of a large range of gold bipyramid sizes, as well as higher aspect ratio nanojavelin ensembles with specific attention to the lowest-order acoustic phonon mode of these nanoparticles. We report coherent phonon-driven oscillations of the LSPR position for particles with resonances spanning 670 to 1330 nm. Nanojavelins were shown to behave similarly to bipyramids but offer the prospect of separate control over LSPR energy and coherent phonon oscillation period. We develop a new methodology for quantitatively measuring mechanical expansion caused by photogenerated coherent phonons. Using this method, we find an elongation of approximately 1% per photon absorbed per unit cell and that particle expansion along the lowest frequency acoustic phonon mode is linearly proportional to excitation fluence for the fluence range studied. These characterizations provide insight regarding means to manipulate phonon period and transient mechanical deformation.

36 MATERIALS SCIENCE↗

Design of high-strength refractory complex solid-solution alloys

Nickel-based superalloys and near-equiatomic high-entropy alloys containing molybdenum are known for higher temperature strength and corrosion resistance. Yet, complex solid-solution alloys offer a huge design space to tune for optimal properties at slightly reduced entropy. For refractory Mo-W-Ta-Ti-Zr, we showcase KKR electronic structure methods via the coherent-potential approximation to identify alloys over five-dimensional design space with improved mechanical properties and necessary global (formation enthalpy) and local (short-range order) stability. Deformation is modeled with classical molecular dynamic simulations, validated from our first-principle data. We predict complex solid-solution alloys of improved stability with greatly enhanced modulus of elasticity (3× at 300 K) over near-equiatomic cases, as validated experimentally, and with higher moduli above 500 K over commercial alloys (2.3× at 2000 K). We also show that optimal complex solid-solution alloys are not described well by classical potentials due to critical electronic effects.

36 MATERIALS SCIENCE↗

Upstreamness and downstreamness in input–output analysis from local and aggregate information

Abstract Ranking sectors and countries within global value chains is of paramount importance to estimate risks and forecast growth in large economies. However, this task is often non-trivial due to the lack of complete and accurate information on the flows of money and goods between sectors and countries, which are encoded in input–output (I–O) tables. In this work, we show that an accurate estimation of the role played by sectors and countries in supply chain networks can be achieved without full knowledge of the I–O tables, but only relying on local and aggregate information, e.g., the total intermediate demand per sector. Our method, based on a rank-1 approximation to the I–O table, shows consistently good performance in reconstructing rankings (i.e., upstreamness and downstreamness measures for countries and sectors) when tested on empirical data from the world input–output database. Moreover, we connect the accuracy of our approximate framework with the spectral properties of the I–O tables, which ordinarily exhibit relatively large spectral gaps. Our approach provides a fast and analytically tractable framework to rank constituents of a complex economy without the need of matrix inversions and the knowledge of finer intersectorial details.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Decreasing the electronic confinement in layered perovskites through intercalation

We show that post-synthetic small-molecule intercalation can significantly reduce the electronic confinement of 2D hybrid perovskites. Using a combined experimental and theoretical approach, we explain structural, optical, and electronic effects of intercalating highly polarizable molecules in layered perovskites designed to stabilize the intercalants. Polarizable molecules in the organic layers substantially alter the optical and electronic properties of the inorganic layers. By calculating the spatially resolved dielectric profiles of the organic and inorganic layers within the hybrid structure, we show that the intercalants afford organic layers that are more polarizable than the inorganic layers. This strategy reduces the confinement of excitons generated in the inorganic layers and affords the lowest exciton binding energy for an n = 1 perovskite of which we are aware. We also demonstrate a method for computationally evaluating the exciton's binding energy by solving the Bethe–Salpeter equation for the exciton, which includes an ab initio determination of the material's dielectric profile across organic and inorganic layers. This new semi-empirical method goes beyond the imprecise phenomenological approximation of abrupt dielectric-constant changes at the organic–inorganic interfaces. This work shows that incorporation of polarizable molecules in the organic layers, through intercalation or covalent attachment, is a viable strategy for tuning 2D perovskites towards mimicking the reduced electronic confinement and isotropic light absorption of 3D perovskites while maintaining the greater synthetic tunability of the layered architecture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Modeling Pion and Nucleon Total Cross-sections

With an eye towards proposed experiments at the LHC, an earlier eikonal mini-jet model with soft gluons has now been extended to compute {pi}p and {pi}{pi} total cross-sections.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Ferromagnetism in neutron matter and its implication for the neutron star equation of state

We investigate the possible contribution of the ferromagnetic phase of neutron matter in the neutron star interior to the star's magnetic field. We introduce a relativistic, self-consistent calculation of the ferromagnetic phase in neutron matter within the context of the relativistic mean-field approximation. The presence of the ferromagnetic phase stiffens the star's equation of state which implies a larger neutron star radius compared to the non-ferromagnetic case.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Electron-vibron coupling in halogenated acenaphthenequinone upon O K-edge soft x-ray absorption

We present high resolution oxygen K near-edge x-ray absorption spectra of the acenaphthenequinone (ANQ) derivative 3,8-dibromo-5,6-dichloro-ANQ (Br{sub 2}Cl{sub 2}-ANQ). The spectral features exhibit an almost identical vibronic fine structure compared to that shown by ANQ. The unequal distances of the vibronic levels as derived from the least-squares fit analysis of the vibronic progressions allows us to determine the anharmonicity of the excited state potentials involved. We conclude that a single vibrational progression couples to the resonant excitation of O 1s core electrons preferentially. Comparison of the two ANQ derivatives gives a clear indication that the vibronic mode corresponds to a C=O stretching mode, rather than coupling to a C-H mode as suggested previously. These conclusions are supported by density functional theory calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗