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At least 757 records · Page 42

High resolution identification and quantification of diffuse deep groundwater discharge in mountain rivers using continuous boat-mounted helium measurements

Discharge of deeply sourced groundwater to streams is difficult to locate and quantify, particularly where both discrete and diffuse discharge points exist, but diffuse discharge is one of the primary controls on solute budgets in mountainous watersheds. The noble gas helium is a unique identifier of deep groundwater discharge because groundwater with long residence times is commonly enriched in helium. In this study, a portable mass spectrometer was used to measure longitudinal variation in dissolved helium concentrations in two mountainous rivers at high spatial resolution not feasible with traditional sampling techniques. Helium profiles were then simulated using a mass-balance model to quantify longitudinal variation in groundwater discharge to the receiving rivers. Results indicate helium concentrations were enriched by multiple orders of magnitude above atmospheric equilibrium in both rivers and that this persisted for up to 18 km below observed pulse inputs in the Colorado River. Helium mass-balance models match observed longitudinal patterns with the exception of sharp initial increases in helium observed in the rivers. Increased longitudinal groundwater discharge rates correspond to mapped geologic structures in both watersheds that likely transport deep geothermal water. Models show variable sensitivity to spatial assignment of input variables representing the groundwater source, illustrating the importance of collecting data from discrete groundwater discharges where possible. The methodology shows promise for field experiments designed to assess air–water exchange rates and to quantify total groundwater discharge from a combination of discrete and diffuse sources.

Deep groundwater↗

Modeling of flash sintering of ionic ceramics

A fundamental understanding of the influence of defects in ionic ceramics at the atomic, microstructural, and macroscopic levels, before, during, and after the flash sintering event is key to the development of ceramic processing operations that lead to fast, low cost, and environmentally safe fabrication of materials. The observed phenomenology of the flash process encompasses multiple time and length scales and have resulted on a wide variety of what sometimes appears to be contradictory explanations. Here, this article summarizes the latest developments on the modeling and simulation of flash sintering, specifically those related to the understanding of the equilibrium and kinetic properties and the corresponding microstructural evolution of ionic ceramics. Challenges and opportunities in the development of theoretical analyses that include unidentified multiphysical effects are discussed, as they pertain to the processing of technologically relevant ceramic materials for advanced structures and devices.

36 MATERIALS SCIENCE↗

A quantitative phase-field model for gas bubble evolution in UO2

Due to the large formation energy of vacancies and noble gas atoms in the form of interstitials or substitutional atoms in nuclear fuel (UO2), the thermodynamic equilibrium concentrations of these species are very low in the nuclear fuel matrix even at very high temperatures, which imposes difficulties upon the quantitative study of bubble evolution via the phase-field method. In this study, a quantitative phase-field model is proposed to deal with this problem. The system’s free energy density is derived according to the principles of thermodynamics, with consideration of the elastic effect and with the use of real material parameters from experiments. The model is useful for the study of the kinetics of gas bubble growth with very dilute concentrations of vacancy and gas atoms in the matrix. This model is applied to study single bubble growth and multiple bubble growth under various concentrations of vacancy and gas atoms and at various temperatures. The elastic effect and the effects of the generation rate of vacancies and gas atoms on bubble growth are analyzed.

low defect concentration, nuclear fuel, gas bubble↗

Time reversal symmetry breaking and odd viscosity in active fluids: Green–Kubo and NEMD results

Active fluids, which are driven at the microscale by non-conservative forces, are known to exhibit novel transport phenomena due to the breaking of time reversal symmetry. Recently, Epstein and Mandadapu [arXiv:1907.10041 (2019)] obtained Green-Kubo relations for the full set of viscous coefficients governing isotropic chiral active fluids, including the so-called odd viscosity, invoking Onsager's regression hypothesis for the decay of fluctuations in active non-equilibrium steady states. In this Communication, we test these Green-Kubo relations using molecular dynamics simulations of a canonical model system consisting of actively torqued dumbbells. We find the resulting odd and shear viscosity values from the Green-Kubo relations to be in good agreement with values measured independently through non-equilibrium molecular dynamics flow simulations. This provides a test of the Green-Kubo relations and lends support to the application of the Onsager regression hypothesis in relation to viscous behaviors of active matter systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Active and Transfer Learning of High-Dimensional Neural Network Potentials for Transition Metals

Classical molecular dynamics (MD) simulations represent a very popular and powerful tool for materials modeling and design. The predictive power of MD hinges on the ability of the interatomic potential to capture the underlying physics and chemistry. There have been decades of seminal work on developing interatomic potentials, albeit with a focus predominantly on capturing the properties of bulk materials. Such physics-based models, while extensively deployed for predicting the dynamics and properties of nanoscale systems over the past two decades, tend to perform poorly in predicting nanoscale potential energy surfaces (PESs) when compared to high-fidelity first-principles calculations. These limitations stem from the lack of flexibility in such models, which rely on a predefined functional form. Machine learning (ML) models and approaches have emerged as a viable alternative to capture the diverse size-dependent cluster geometries, nanoscale dynamics, and the complex nanoscale PESs, without sacrificing the bulk properties. Here, in this study, we introduce an ML workflow that combines transfer and active learning strategies to develop high-dimensional neural networks (NNs) for capturing the cluster and bulk properties for several different transition metals with applications in catalysis, microelectronics, and energy storage, to name a few. Our NN first learns the bulk PES from the high-quality physics-based models in literature and subsequently augments this learning via retraining with a higher-fidelity first-principles training data set to concurrently capture both the nanoscale and bulk PES. Our workflow departs from status-quo in its ability to learn from a sparsely sampled data set that nonetheless covers a diverse range of cluster configurations from near-equilibrium to highly nonequilibrium as well as learning strategies that iteratively improve the fingerprinting depending on model fidelity. All the developed models are rigorously tested against an extensive first-principles data set of energies and forces of cluster configurations as well as several properties of bulk configurations for 10 different transition metals. Our approach is material agnostic and provides a methodology to transfer and build upon the learnings from decades of seminal work in molecular simulations on to a new generation of ML-trained potentials to accelerate materials discovery and design.

36 MATERIALS SCIENCE↗

Non-equilibrium rate theory for polariton relaxation dynamics

We derive an analytic expression of the non-equilibrium Fermi’s golden rule (NE-FGR) expression for a Holstein–Tavis–Cumming Hamiltonian, a universal model for many molecules collectively coupled to the optical cavity. These NE-FGR expressions capture the full-time-dependent behavior of the rate constant for transitions from polariton states to dark states. The rate is shown to be reduced to the well-known frequency domain-based equilibrium Fermi’s golden rule (E-FGR) expression in the equilibrium and collective limit and is shown to retain the same scaling with the number of sites in non-equilibrium and non-collective cases. We use these NE-FGR to perform population dynamics with a time-non-local and time-local quantum master equation and obtain accurate population dynamics from the initially occupied upper or lower polariton states. Furthermore, NE-FGR significantly improves the accuracy of the population dynamics when starting from the lower polariton compared to the E-FGR theory, highlighting the importance of the non-Markovian behavior and the short-time transient behavior in the transition rate constant.

Chemical dynamics↗

Assessment of Performance of Density Functionals for Predicting Potential Energy Curves in Hydrogen Storage Applications

We report the availability of accurate computational tools for modeling and simulation is vital to accelerate the discovery of materials capable of storing hydrogen (H 2 ) under given parameters of pressure swing and temperature. Previously, we compiled the H2Bind275 data set consisting of equilibrium geometries and assessed the performance of 55 density functionals over this data set (Veccham, S. P.; Head-Gordon, M. J. Chem. Theory Comput. 2020, 16, 4963-4982). As it is crucial for computational tools to accurately model the entire potential energy curve (PEC), in addition to the equilibrium geometry, we extended this data set with 389 new data points to include two compressed and three elongated geometries along 78 PECs for H 2 binding, forming the H2Bind78 × 7 data set. By assessing the performance of 55 density functionals on this significantly larger and more comprehensive H2Bind78 × 7 data set, we identified the best performing density functionals for H 2 binding applications: PBE0-DH, ωB97X-V, ωB97M-V, and DSD-PBEPBE-D3(BJ). The addition of Hartree-Fock exchange improves the performance of density functionals, albeit not uniformly throughout the PEC. We recommend the usage of ωB97X-V and ωB97M-V density functionals as they offer good performance for both geometries and energies. In addition, we also identified B97M-V and B97M-rV as the best semilocal density functionals for predicting H 2 binding energy at its equilibrium geometry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Analysis of MHD stability and active mode control on KSTAR for high confinement, disruption-free plasma

Long-pulse plasma operation at high normalized beta, $β_N$, above the $\textit{n}$= 1 ideal MHD no-wall stability limit in KSTAR is presently limited by tearing instabilities rather than resistive wall modes. H-mode plasma operation during the recent KSTAR device campaign produced discharges having strong $\textit{m/n}$= 2/1 tearing instabilities at $β_N$ lower than the ideal MHD no-wall beta limit. The unstable tearing mode consequently reduced plasma confinement and toroidal plasma rotation significantly. We report the experiment confirmed that an extended duration of electron cyclotron heating (ECH) at the initial phase of the discharge plays a critical role in mode destabilization. To study destabilizing mechanisms that affect the mode growth, the stability of the observed tearing modes from plasmas with significantly different $β_N$ is computed by using the resistive DCON code and the M3D-C 1 code. Equilibrium reconstructions that include constraints from internal profile diagnostics, and computed fast particle pressure are used as input for reliable computation of stability. The classical tearing stability index, Δ', from resistive DCON is computed to be unstable when the island is fully saturated with large amplitude, while the unstable mode is not computed by M3D-C 1 . The modified Rutherford equation (MRE) describing the evolution of the island width has been constructed for KSTAR plasmas by using plasma parameters computed by the TRANSP code. The MRE model estimates a saturated island width corresponding to ~10% of the plasma minor radius for equilibrium at high $β_N$ 3 having a stable Δ' from the resistive DCON. In preparation for long-pulse plasma operation at higher beta utilizing increased plasma heating power, a resistive wall mode (RWM) active feedback control algorithm has been completed and enabled on KSTAR. To accurately determine the $\textit{n}$= 1component produced by RWMs, an algorithm has been developed that includes magnetic sensor compensation of the prompt applied field and the field from the induced current on the passive conductors. Use of multiple toroidal sensor arrays is enabled by modifying the sensor toroidal angles assumed in mode decomposition to include the effect of varied mode helicities in the outboard region where the mode measurement is made. This analysis on stability, transport, and control provides the required foundation for disruption prediction and avoidance research on KSTAR.

resistive wall mode (RWM)↗

Integration of graphical approaches into optimization-based design of multistage liquid extraction

We propose two optimization models for designing two liquid extraction systems: simple multistage liquid extractors and extractors with extract reflux. Both models are motivated by the concepts of the modified McCabe-Thiele graphical method for multistage extractor design. The operating and equilibrium curves in the McCabe-Thiele method are represented by material balances and piece-wise linearized thermodynamics properties. The use of piece-wise approximations improves computational tractability of both optimization models. In addition, we consider some extensions such as dilute systems, insoluble solvents, and non-ideal stages. In conclusion, the applicability of the proposed models is demonstrated with four illustrative examples.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Parameter Study of the Running-In Process for the Generic Pebble Bed Reactor (GPBR200)

The run-in period of a pebble bed reactor is complex and difficult to model given significant heterogeneity in core composition, power, and temperature. While it is understood that the initial composition of the core should eventually result in the same equilibrium core composition, the approach to equilibrium can vary significantly depending on factors such as start-up fuel enrichment and power ramp rate. To explore this, a high-fidelity model of the General Pebble Bed Reactor was used to vary power ramp schemes and start-up core compositions. It was found that both the initial core composition and power ramp rate had a significant impact on the flow rate of pebbles during early time steps, with higher ramp rates and low enrichment resulting in non-physical flow rates. Power ramp rate alone was found to dictated maximum pebble power peaking observed during the run-in process, with higher ramp rates resulting in greater peak pebble powers. Start-up fuel enrichment and power ramp were found to both impact total fuel consumption, although the impact of start-up fuel enrichment was generally secondary to ramp rate.

22 - GENERAL STUDIES OF NUCLEAR REACTORS↗

Catalyzed baryogenesis

A novel mechanism, “catalyzed baryogenesis”, is proposed to explain the observed baryon asymmetry in our universe. In this mechanism, the motion of a ball-like catalyst provides the necessary out-of-equilibrium condition, its outer wall has CP-violating interactions with the Standard Model particles, and its interior has baryon number violating interactions. We use the electroweak-symmetric ball model as an example of such a catalyst. In this model, electroweak sphalerons inside the ball are active and convert baryons into leptons. The observed baryon number asymmetry can be produced for a light ball mass and a large ball radius. Due to direct detection constraints on relic balls, we consider a scenario in which the balls evaporate, leading to dark radiation at testable levels.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Chiral assemblies of pinwheel superlattices on substrates

The unique topology and physics of chiral superlattices make their self-assembly from nanoparticles highly sought after yet challenging in regard to (meta)materials. In this report we show that tetrahedral gold nanoparticles can transform from a perovskite-like, low-density phase with corner-to-corner connections into pinwheel assemblies with corner-to-edge connections and denser packing. Whereas corner-sharing assemblies are achiral, pinwheel superlattices become strongly mirror asymmetric on solid substrates as demonstrated by chirality measures. Liquid-phase transmission electron microscopy and computational models show that van der Waals and electrostatic interactions between nanoparticles control thermodynamic equilibrium. Variable corner-to-edge connections among tetrahedra enable fine-tuning of chirality. The domains of the bilayer superlattices show strong chiroptical activity as identified by photon-induced near-field electron microscopy and finite-difference time-domain simulations. The simplicity and versatility of substrate-supported chiral superlattices facilitate the manufacture of metastructured coatings with unusual optical, mechanical and electronic characteristics.

42 ENGINEERING↗

Percolation and nanosecond fluctuators in V 2 O 3 films within the metal–insulator transition

Vanadium sesquioxide (V 2 O 3 ) exhibits a metal–insulator transition (MIT) at 160 K between a low temperature, monoclinic, antiferromagnetic Mott insulator and a high temperature, rhombohedral, paramagnetic, metallic phase. In thin films, a percolative transition takes place over a finite temperature range of phase coexistence. We study the fluctuating dynamics of this percolative MIT by measuring voltage noise spectra at both low frequencies (up to 100 kHz) and radio frequencies (between 10 MHz and 1 GHz). Noise intensity quadratic in bias is observed in the MIT region, as expected for resistive fluctuations probed nonperturbatively by the current. The low frequency noise resembles flicker-type 1/f β noise, often taking on the form of Lorentzian noise dominated by a small number of fluctuators as the volume fraction of the insulating phase dominates. Radio frequency noise intensity also quadratic in the bias current allows the identification of resistance fluctuations with lifetimes below 1 ns, approaching timescales seen in non-equilibrium pump–probe studies of the transition. We find quantitative consistency with a model for fluctuations in the percolative fraction. The thermodynamics of the MIT suggests that dominant fluctuations are ones that alter small volumes affecting the connectivity of domain boundaries. This noise serves as a sensitive and nonperturbative probe for the dynamics of switching phenomena in this system.

36 MATERIALS SCIENCE↗

Phase change materials for thermal energy storage: A perspective on linking phonon physics to performance

Thermal energy storage is being actively investigated for grid, industrial, and building applications for realizing an all-renewable energy world. Phase change materials (PCMs), which are commonly used in thermal energy storage applications, are difficult to design because they require excellent energy density and thermal transport, both of which are difficult to predict from simple physics-based models. In this Perspective, we describe recent advances in the understanding of the equilibrium and transport properties of PCM materials that can help accelerate technology development. We then emphasize how the microscopic phonon picture of both liquids and solids enables a better understanding of novel PCM systems and their predictive power. Here, we then show how this microscopic picture can be used to understand kinetic processes, such as supercooling, and how it can impact the thermal power output in thermal energy storage systems.

25 ENERGY STORAGE↗

Excited-state potentials for modelling dense plasmas from first principles

The modelling of dense plasmas using finite-temperature density functional theory has proven very successful in determining transport properties and the equation of state of systems where quantum many-body effects and correlations play a key role in their structure. Here we show how excited-state projector augmented- wave potentials can be used to extend these calculations to explicitly model core-hole states, allowing for the calculation of the electronic structure of a range of integer charge configurations embedded in a dense plasma environment. Our excited-state potentials show good agreement with all-electron calculations at finite-temperatures, motivating their use as an efficient approach in modelling from first principles both the structure of strongly-coupled non-equilibrium plasmas and their interaction with intense X-rays.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Fermion mass, axion dark matter, and leptogenesis in SO(10) GUT

SO(10) grand unified theory with minimum parameters in the Yukawa sector employs the Peccei-Quinn symmetry that solves the strong C P problem. Such an economical Yukawa sector is highly appealing and has been extensively studied in the literature. However, when the running of the renormalization group equations of the Yukawa couplings are considered, this scenario shows some tension with the observed fermion masses and mixing. In this work, we propose an extension of the minimal framework that utilizes lower dimensional representations and alleviates this tension by introducing only a few new parameters. The proposed model consists of a fermion in the fundamental and a scalar in the spinorial representations. While the latter is needed to implement the Peccei-Quinn symmetry successfully, the presence of both is essential in obtaining an excellent fit to the fermion mass spectrum. In our model, axions serve the role of dark matter, and the out-of-equilibrium decays of the right-handed neutrinos successfully generate the matter-antimatter symmetry of the Universe. Published by the American Physical Society 2024

Astronomy & Astrophysics↗

Coordinated Market Design for Peer-to-Peer Energy Trade and Ancillary Services in Distribution Grids

A novel peer-to-peer (P2P) market design is proposed in this work for the distribution grid level. Envisioning that the grid constraints violations are the major challenge for P2P energy sharing, we propose they are handled through the ancillary service (AS) market. By calculating the decomposable distribution locational marginal prices (DLMPs), the essential price signals of procuring AS can be recovered to determine the grid usage prices (GUPs) to each P2P transaction. Hence, the GUPs, due to their decomposable properties, act as incentive signals for the P2P market to support the grid operation in terms of loss reduction, voltage support and congestion management. The proposed market design comprises: i) an interactive market design of P2P trade & AS and, ii) a fully decentralized peer-centric market clearing model for P2P energy trade. The duality analysis provides the composition of market equilibrium prices of P2P trading and their interpretations. The case studies demonstrate the effectiveness of the proposed P2P trade to support grid operational objectives.

Zhang, Kai↗

Crystallization histories of the group IIF iron meteorites and Eagle Station pallasites

The group IIF iron meteorites and Eagle Station pallasites (PES) have highly siderophile element abundances (HSE; Re, Os, Ir, Ru, Pt, and Pd) of metal that are consistent with formation in planetesimal cores by fractional crystallization with minor to major solid metal-liquid metal mixing. Modeling of HSE abundances of the IIF irons indicates a complex formation history that included the mixing of primitive and evolved solid and liquid metals. By contrast, modeling of HSE abundances of PES metal suggests these meteorites formed mainly as equilibrium solids from a common liquid. Abundances of some of the siderophile elements in the IIF irons and PES are permissive of a common core origin, however, the abundances of W and Ni indicate the PES ultimately formed on a more oxidized body. The PES most likely formed by the injection of olivine present at the core-mantle boundary into a metallic core liquid as a result of impact. The core then crystallized inward, trapping the olivine.

58 GEOSCIENCES↗