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At least 667 records · Page 37

Mass-conserving implicit–explicit methods for coupled compressible Navier–Stokes equations

Earth system models are composed of coupled components that separately model systems such as the global atmosphere, ocean, and land surface. While these components are well developed, coupling them in a single system can be a significant challenge. Computational efficiency, accuracy, and stability are principal concerns. In this study we focus on these issues. In particular, implicit–explicit (IMEX) tight and loose coupling strategies are explored for handling different time scales. For a simplified model for the air–sea interaction problem, we consider coupled compressible Navier–Stokes equations with an interface condition. Under the rigid-lid assumption, horizontal momentum and heat flux are exchanged through the interface. Several numerical experiments are presented to demonstrate the stability of the coupling schemes. Here, we show both numerically and theoretically that our IMEX coupling methods are mass conservative for a coupled compressible Navier–Stokes system with the rigid-lid condition

42 ENGINEERING↗

Evaluation of accuracy and convergence of numerical coupling approaches for poroelasticity benchmark problems

Accurate modeling of subsurface flow and transport processes is vital as the prevalence of subsurface activities such as carbon sequestration, geothermal recovery, and nuclear waste disposal increases. Computational modeling of these problems leverages poroelasticity theory, which describes coupled fluid flow and mechanical deformation. Although fully coupled monolithic schemes are accurate for coupled problems, they can demand significant computational resources for large problems. In this work, a fixed stress scheme is implemented into the Sandia Sierra Multiphysics toolkit. Two implementation methods, along with the fully coupled method, are verified with one-dimensional (1D) Terzaghi, 2D Mandel, and 3D Cryer sphere benchmark problems. The impact of a range of material parameters and convergence tolerances on numerical accuracy and efficiency was evaluated. Overall the fixed stress schemes achieved acceptable numerical accuracy and efficiency compared to the fully coupled scheme. However, the accuracy of the fixed stress scheme tends to decrease with low permeable cases, requiring the finer tolerance to achieve a desired numerical accuracy. For the fully coupled scheme, high numerical accuracy was observed in most of cases except a low permeability case where an order of magnitude finer tolerance was required for accurate results. Finally, a two-layer Terzaghi problem and an injection–production well system were used to demonstrate the applicability of findings from the benchmark problems for more realistic conditions over a range of permeability. Simulation results suggest that the fixed stress scheme provides accurate solutions for all cases considered with the proper adjustment of the tolerance. Furthermore, this work clearly demonstrates the robustness of the fixed stress scheme for coupled poroelastic problems, while a cautious selection of numerical tolerance may be required under certain conditions with low permeable materials.

58 GEOSCIENCES↗

FEM-BEM coupling methods for Tokamak plasma axisymmetric free-boundary equilibrium computations in unbounded domains

Incorporating boundary conditions at infinity into simulations on bounded computational domains is a repeatedly occurring problem in scientific computing. The combination of finite element methods (FEM) and boundary element methods (BEM) is the obvious instrument, and we adapt here for the first time the two standard FEM-BEM coupling approaches to the free-boundary equilibrium problem: the Johnson–Nédélec coupling and the Bielak–MacCamy coupling. We recall also the classical approach for fusion applications, dubbed according to its first appearance von-Hagenow–Lackner coupling and present the less used alternative introduced by Albanese, Blum and de Barbieri in . We show that the von-Hagenow–Lackner coupling suffers from undesirable non-optimal convergence properties, that suggest that other coupling schemes, in particular Johnson–Nédélec or Albanese–Blum–de Barbieri are more appropriate for non-linear equilibrium problems. Moreover, we show that any of such coupling methods requires Newton-like iteration schemes for solving the corresponding non-linear discrete algebraic systems.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Simultaneous Activation of CH4 and CO2 for Concerted C-C Coupling at the Oxide-Oxide Interfaces

Catalytic conversion of CO2 and CH4 to value-added platform chemicals via the direct C-C coupling provides one of the most effective routes that not only address global climate change but also alleviate the dependency on traditional fossil fuels. Herein, three oxide-on-oxide catalysts that can realize direct C-C coupling on the basis of simultaneous activation of CH4 and CO2 were investigated using density functional theory (DFT) calculations. With the formation of oxide-on-oxide interfacial sites between the substrate (In2O3) and dispersed oxides ((ZnO)3, (ZrO2)3, or Ga2O3), it is found that CO2 can be activated at the defective site of In2O3 while the C-H bond of CH4 can be simultaneously activated at the M-O pair of the supported metal oxide. In contrast to the Eley-Rideal mechanism that C-C coupling of CO2 and CH3 stabilized on Zn-doped ceria follows, the formation of a Zn-C-C-O transition state at the active centers originates from a Langmuir-Hinshelwood mechanism where the activated CO2 also enhances the dissociative adsorption of CH4. There is a linear relationship between the C-C coupling reaction energy/activation barrier and CH4 dissociation energy. The results indicate that dissociative adsorption of CH4 plays a dominant role in the direct C-C coupling, whereas the adsorption/activation of CO2 is less significant. DFT calculation results of CH4 and CO2 to acetic acid on the (ZnO)3/In2O3 catalyst surface indicates that the C-C coupling step is the kinetically most relevant step. Compared with Ga2O3/In2O3 and (ZrO2)3/In2O3 catalyst surfaces, (ZnO)3/In2O3(110) is more active for the acetic acid formation. The present work provides new mechanistic insights into the direct C-C coupling of CH4 and CO2, which would be useful to design more efficient catalyst.

CH4 activation, C-C coupling, supported oxides, In↗

Climatology of Cloud‐Land‐Surface Coupling Across Different ARM Sites

Land-atmosphere interactions play a critical role in the evolution and formation of low-level clouds. The different states of coupling between low-level clouds and the surface are uncertain, primarily over continental regions, where complex thermodynamics complicates their investigation. This study uses observations from the Atmospheric Radiation Measurement User Facility to explore cloud-surface coupling and perform a climatological analysis of this interaction in five countries across three continents. The results reveal consistent coupling thresholds and average percentages across the five sites, with coupled clouds accounting for 66% of the cases and decoupled clouds for 34%. Thermodynamic and dynamic evaluations show distinct differences between coupled and decoupled clouds. Coupled clouds are characterized by humid environments, in which vertical motions connect the surface and lower atmosphere to the cloud base, conditions that favor the formation of boundary layer clouds. Decoupled clouds prefer to occur in a drier and colder environment with vertical motions inside the boundary layer being detached from the cloud base, under which boundary layer clouds are hard to form. Coupled clouds peak during warmer hours and seasons, and vice versa for decoupled clouds. This study underscores the complexity of cloud-land-surface interactions and paves the way for further investigations into cloud formation and evolution under different atmospheric environments.

54 ENVIRONMENTAL SCIENCES↗

On the nature of long range electronic coupling in a medium: Distance and orientational dependence for chromophores in molecular aggregates

The electronic coupling that mediates energy transfer in molecular aggregates is theoretically investigated using the principles of quantum electrodynamics (QED). In this context, both the electromagnetic tensor and rate equation relating to these couplings are re-examined with a focus on the role of the relative distance and orientation of transition dipole moment pairs, considering near-, intermediate-, and far-zone contributions to the coupling. The QED based coupling terms are investigated both analytically and numerically, and they are physically interpreted in terms of the character of the mediating (virtual) photons. The spatial dependence of the couplings for a two-dimensional molecular aggregate of ordered and isotropic transition dipole moments is numerically calculated. Further, Pauli Master Equations are employed for a one-dimensional chain of molecules and donor-acceptor pairs, to investigate the importance of intermediate- and far-zone contributions to the electronic coupling on electronic energy transfer dynamics. The results indicate that although Förster theory is often qualitatively and quantitatively correct for describing electronic energy transfer (EET) processes, intermediate- and far-zone coupling terms could sometimes be non-negligible for correctly describing EET in natural and artificial, mesoscopic, solar energy harvesting systems. In particular, the results indicate that these terms are non-negligible when using Förster resonance energy transfer spectroscopic ruler techniques for distances >10 nm.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Exciton delocalization, charge transfer, and electronic coupling for singlet excitation energy transfer between stacked nucleobases in DNA: An MS-CASPT2 study

Exciton delocalization and singlet excitation energy transfer have been systematically studied for the complete set of 16 DNA nucleobase dimers in their ideal, single-strand stacked B-DNA conformation, at the MS-CASPT2 level of theory. The extent of exciton delocalization in the two lowest (π,π{sup *}) states of the dimers is determined using the symmetrized one-electron transition density matrices between the ground and excited states, and the electronic coupling is calculated using the delocalization measure and the energy splitting between the states [see F. Plasser, A. J. A. Aquino, W. L. Hase, and H. Lischka, J. Phys. Chem. A 116, 11151–11160 (2012)]. The calculated couplings lie between 0.05 eV and 0.14 eV. In the B-DNA conformation, where the interchromophoric distance is 3.38 Å, our couplings deviate significantly from those calculated with the transition charges, showing the importance of orbital overlap components for the couplings in this conformation. The calculation of the couplings is based on a two-state model for exciton delocalization. However, in three stacks with a purine in the 5{sup ′} position and a pyrimidine in the 3{sup ′} one (AT, GC, and GT), there is an energetically favored charge transfer state that mixes with the two lowest excited states. In these dimers we have applied a three-state model that considers the two locally excited diabatic states and the charge transfer state. Using the delocalization and charge transfer descriptors, we obtain all couplings between these three states. Our results are important in the context of DNA photophysics, since the calculated couplings can be used to parametrize effective Hamiltonians to model extended DNA stacks. Our calculations also suggest that the 5{sup ′}-purine-pyrimidine-3{sup ′} sequence favors the formation of charge transfer excited states.

74 ATOMIC AND MOLECULAR PHYSICS↗

Electronic coupling calculations with transition charges, dipoles, and quadrupoles derived from electrostatic potential fitting

A transition charge, dipole, and quadrupole from electrostatic potential (TrESP-CDQ) method for electronic coupling calculations is proposed. The TrESP method is based on the classical description of electronic Coulomb interaction between transition densities for individual molecules. In the original TrESP method, only the transition charge interactions were considered as the electronic coupling. In the present study, the TrESP method is extended to include the contributions from the transition dipoles and quadrupoles as well as the transition charges. Hence, the self-consistent transition density is employed in the ESP fitting procedure. To check the accuracy of the present approach, several test calculations are performed to a helium dimer, a methane dimer, and an ethylene dimer. As a result, the TrESP-CDQ method gives a much improved description of the electronic coupling, compared with the original TrESP method. The calculated results also show that the self-consistent treatment to the transition densities contributes significantly to the accuracy of the electronic coupling calculations. Based on the successful description of the electronic coupling, the contributions to the electronic coupling are also analyzed. This analysis clearly shows a negligible contribution of the transition charge interaction to the electronic coupling. Hence, the distribution of the transition density is found to strongly influence the magnitudes of the transition charges, dipoles, and quadrupoles. The present approach is useful for analyzing and understanding the mechanism of excitation-energy transfer.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The role of weak interlayer coupling in the spin-reorientation of perpendicular ultrathin Co-Fe-B/MgO-based heterostructures

Ultrathin magnetic tunneling structures implicate fundamental interlayer exchange coupling between magnetic layers. Here, we describe its important role in the spin-reorientation transition of weakly coupled perpendicular ultrathin Ta/Co-Fe-B/MgO/Co-Fe-B/Ta heterostructures. Near the spin-reorientation, the domain structure is quite sensitive to weak interlayer exchange coupling. Antiferromagnetic coupling stabilizes homogeneous perpendicular magnetization at the remanence, whereas ferromagnetic coupling favors in-/out-of-plane stripe domains. Close to the spin-reorientation transition, even the subtle changes of interlayer exchange coupling can lead to reversible switching between stable in- and out-of-plane states. Our results suggest that this multi-stability caused by the interplay of perpendicular anisotropy and weak interlayer coupling can be utilized in perpendicular spin torque devices operating under reduced spin currents.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Optomechanical coupling in phoxonic–plasmonic slab cavities with periodic metal strips

We theoretically investigate the optomechanical (OM) coupling of submicron cavities formed in one-dimensional phoxonic–plasmonic slabs. The phoxonic–plasmonic slabs are structured by depositing periodic Ag strips onto the top surfaces of dielectric GaAs slabs to produce dual band gaps for both electromagnetic and acoustic waves, thereby inducing the coupling of surface plasmons with photons for tailoring the OM coupling. We quantify the OM coupling by calculating the temporal modulation of the optical resonance wavelength with the acoustic phonon-induced photoelastic (PE) and moving-boundary (MB) effects. We also consider the appearance of a uniform Ag layer on the bottom surface of the slabs to modulate the photonic–plasmonic coupling. The results show that the PE and MB effects can be constructive or destructive in the overall OM coupling, and their magnitudes depend not only on the quality factors of the resonant modes but also on the mode area, mode overlap, and individual symmetries of the photonic–phononic mode pairs. Lowering the mode area could be effective for enhancing the OM coupling of subwavelength photons and phonons. This study introduces possible engineering applications to achieve enhanced interaction between photons and phonons in nanoscale OM devices.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Towards a global model of spin-orbit coupling in the halocarbenes

We report a global analysis of spin-orbit coupling in the mono-halocarbenes, CH(D)X, where X = Cl, Br, and I. These are model systems for examining carbene singlet-triplet energy gaps and spin-orbit coupling. Over the past decade, rich data sets collected using single vibronic level emission spectroscopy and stimulated emission pumping spectroscopy have yielded much information on the ground vibrational level structure and clearly demonstrated the presence of perturbations involving the low-lying triplet state. To model these interactions globally, we compare two approaches. First, we employ a diabatic treatment of the spin-orbit coupling, where the coupling matrix elements are written in terms of a purely electronic spin-orbit matrix element which is independent of nuclear coordinates, and an integral representing the overlap of the singlet and triplet vibrational wavefunctions. In this way, the structures, harmonic frequencies, and normal mode displacements from ab initio calculations were used to calculate the vibrational overlaps of the singlet and triplet state levels, including the full effects of Duschinsky mixing. These calculations have allowed many new assignments to be made, particularly for CHI, and provided spin-orbit coupling parameters and values for the singlet-triplet gaps. In a second approach, we have computed and fit full geometry dependent spin-orbit coupling surfaces and used them to compute matrix elements without the product form approximation. Those matrix elements were used in similar fits varying the anharmonic constants and singlet-triplet gap to reproduce the experimental levels. The derived spin-orbit parameters for carbenes CHX (X = Cl, Br, and I) show an excellent linear correlation with the atomic spin-orbit constant of the corresponding halogen, indicating that the spin-orbit coupling in the carbenes is consistently around 14% of the atomic value.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Generic Multi-Frequency Modelling of Converter-Connected Renewable Energy Generators Considering Frequency and Sequence Couplings

Frequency and sequence couplings can compromise the trustworthiness of multi-frequency models for converter-based systems. There have been effective attempts to address the couplings mainly by linearized averaged models. Only a few studies have been conducted on practical optimization of such models with enormous matrices and experimental results. This paper provides a generic theory for coupling patterns and proposes a multi-frequency modelling method to detect and address only the main couplings in the sequence domain for converter-connected renewable energy generators. The proposed generic model is based on empirical tests using small-signal perturbations and adopting Fourier transform on the switching converter response. The proposed theory and modelling methodology are verified using a 7MVA grid emulator for voltage perturbation tests on a 2MVA photo-voltaic converter. Accordingly, the couplings can exist in more generic forms, including multiples of perturbation and fundamental frequencies. To the best of our knowledge, the patterns with the multiples of the perturbation frequency have been overlooked in the literature. Furthermore, the mirror frequency concept is valid for all coupling patterns and is included in the proposed model. Besides, the proposed patterns and the environment noise levels have been practical criteria for selecting the main couplings.

frequency and sequence couplings↗

Ocean-Atmosphere Coupled Model Simulations of Precipitation in the Central Andes

The meridional extent and complex orography of the South American continent contributes to a wide diversity of climate regimes ranging from hyper-arid deserts to tropical rainforests to sub-polar highland regions. In addition, South American meteorology and climate are also made further complicated by ENSO, a powerful coupled ocean-atmosphere phenomenon. Modelling studies in this region have typically resorted to either atmospheric mesoscale or atmosphere-ocean coupled global climate models. The latter offers full physics and high spatial resolution, but it is computationally inefficient typically lack an interactive ocean, whereas the former offers high computational efficiency and ocean-atmosphere coupling, but it lacks adequate spatial and temporal resolution to adequate resolve the complex orography and explicitly simulate precipitation. Explicit simulation of precipitation is vital in the Central Andes where rainfall rates are light (0.5-5 mm hr-1), there is strong seasonality, and most precipitation is associated with weak mesoscale-organized convection. Recent increases in both computational power and model development have led to the advent of coupled ocean-atmosphere mesoscale models for both weather and climate study applications. These modelling systems, while computationally expensive, include two-way ocean-atmosphere coupling, high resolution, and explicit simulation of precipitation. In this study, we use the Coupled Ocean-Atmosphere-Wave-Sediment Transport (COAWST), a fully-coupled mesoscale atmosphere-ocean modeling system. Previous work has shown COAWST to reasonably simulate the entire 2003-2004 wet season (Dec-Feb) as validated against both satellite and model analysis data when ECMWF interim analysis data were used for boundary conditions on a 27-9-km grid configuration (Outer grid extent: 60.4S to 17.7N and 118.6W to 17.4W).

Regional Climate Model↗

Fully vs. Sequentially Coupled Loads Analysis of Offshore Wind Turbines

The design and analysis methods for offshore wind turbines must consider the aerodynamic and hydrodynamic loads and response of the entire system (turbine, tower, substructure, and foundation) coupled to the turbine control system dynamics. Whereas a fully coupled (turbine and support structure) modeling approach is more rigorous, intellectual property concerns can preclude this approach. In fact, turbine control system algorithms and turbine properties are strictly guarded and often not shared. In many cases, a partially coupled analysis using separate tools and an exchange of reduced sets of data via sequential coupling may be necessary. In the sequentially coupled approach, the turbine and substructure designers will independently determine and exchange an abridged model of their respective subsystems to be used in their partners' dynamic simulations. Although the ability to achieve design optimization is sacrificed to some degree with a sequentially coupled analysis method, the central question here is whether this approach can deliver the required safety and how the differences in the results from the fully coupled method could affect the design. This work summarizes the scope and preliminary results of a study conducted for the Bureau of Safety and Environmental Enforcement aimed at quantifying differences between these approaches through aero-hydro-servo-elastic simulations of two offshore wind turbines on a monopile and jacket substructure.

17 WIND ENERGY↗

Verification and Validation Activities of Molten Salt Reactors Multiphysics Coupling Schemes at Idaho National Laboratory

This paper presents the latest verification and validation activities in molten salt reactor modeling and simulation performed at Idaho National Laboratory. Multiphysics solutions are obtained by coupling the neutronics code Griffin, the thermal hydraulics code Pronghorn, and the system analysis code SAM, under the MOOSE framework. We present various multiphysics coupling schemes with these codes for molten salt reactor problems and provide verification and validation results. First, we present verification test results of the Griffin-Pronghorn coupled scheme for the CNRS benchmark. Then validation test results are presented for the Griffin-SAM coupled scheme for the pump startup and coast down transients of the Molten Salt Reactor Experiment. Finally, the Griffin-Pronghorn-SAM coupled scheme is demonstrated for the Molten Salt Reactor Experiment reactivity insertion transient using a domain-overlapping coupling algorithm between Pronghorn and SAM. The results of these various coupling schemes demonstrate the ability to capture the effect of fuel flow and the various feedback mechanisms important to MSRs.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Anharmonic Cation–Anion Coupling Dynamics Assisted Lithium‐Ion Diffusion in Sulfide Solid Electrolytes

Abstract Sulfide‐based lithium superionic conductors often show higher Li‐ion conductivity than other types of electrolyte materials. This work unveils a unique Li‐ion conductive behavior in these materials through the perspective of anharmonic coupling assisted Li‐ion diffusion. Li hopping events can happen simultaneously with various types of lattice dynamics, while only a statistically important synchronization of motions may indicate coupling. This method enables a direct evaluation of the coupling strength between these motions, which more fundamentally decides if a specific type of lattice motion is really anharmonically coupled to the Li hopping event and whether the coupling can facilitate the Li diffusion. By a new ab initio computational approach, this work unveils a unique phenomenon in prototype sulfide electrolytes in comparison with typical halide ones, that Li‐ion conduction can be boosted by the anharmonic coupling of low‐frequency Li phonon modes with high‐frequency anion stretching or flexing phonon modes, rather than the low‐frequency rotational modes. The coupling pushes Li ions toward the diffusion channels for reduced diffusion barriers. The result from the lower temperature range (≈0–300 K) of simulation can also be more relevant to the application of solid‐state batteries.

Chemistry↗

Global brain activity and its coupling with cerebrospinal fluid flow is related to tau pathology

Abstract INTRODUCTION Factors responsible for the deposition of pathological tau in the brain are incompletely understood. This study links macroscale tau deposition in the human brain to cerebrospinal fluid (CSF) flow dynamics using resting‐state functional magnetic resonance imaging (rsfMRI). METHODS Low‐frequency (< 0.1 Hz) resting‐state global brain activity is coupled with CSF flow and potentially reflects CSF dynamics‐related clearance. We examined the correlation between rsfMRI measures of CSF inflow and global activity (gBOLD–CSF coupling) as a predictor, interacting with amyloid beta (Aβ), of tau and cortical thickness (dependent variables) across Alzheimer's Disease Neuroimaging Initiative (ADNI) participants from cognitively unimpaired through mild cognitive impairment (MCI) and Alzheimer's disease (AD). RESULTS Tau deposition in Aβ+ participants, accompanied by cortical thinning and cognitive decline, is associated with decreased gBOLD–CSF coupling. Tau mediates the relationship between coupling and thickness. DISCUSSION Findings suggest that resting‐state global brain activity and CSF movements comodulate Alzheimer's tau deposition, presumably related to CSF clearance. Highlights A non‐invasive functional magnetic resonance imaging (fMRI) assessment of a CSF clearance‐related process is carried out. Global brain activity is coupled with CSF inflow in human fMRI during resting state. Global fMRI–CSF coupling is correlated with tau in Alzheimer's disease (AD). This coupling measure is also associated with cortical thickness, mediated by tau.

Neurosciences & Neurology↗

Coupling of Independent Electrochemical Reactions and Fluorescence at Closed Bipolar Interdigitated Electrode Arrays

Electrochemical reactions occurring at the opposite ends of bipolar electrodes (BPEs) are necessarily coupled, enabling electron transfer events at one end to be read out optically, for example, by coupling to fluorogenic reactions at the other end. In order to explore the potential of this technique for studying multiple redox events, arrays of parallel BPE interdigitated electrode arrays (IDEAs) were fabricated and integrated with separate analytical and reporter microfluidic channels, respectively, in a closed BPE configuration. The apparatus was initially evaluated employing Fe(CN) 6 3/4- in the analytical channel coupled to weakly emissive resazurin and strongly emissive resorufin as the fluorogenic redox reporter pair. We then used the device to investigate a proton-coupled electron transfer reaction, hydroquinone (QH 2 ) oxidation, in structures with an integrated pH modulation electrode (PME). A pH-sensitive dye, fluorescein, was co-introduced into the analytical channel to monitor PME modulation of solution pH, and its coupling to QH 2 oxidation, thereby permitting changes in solution pH, and consequently QH 2 oxidation rate, to be monitored directly in the analytical channel and compared to the fluorescence in the reporter channel. Additionally, diffusion of OH - generated at the PME produced a spatial pH profile that was visualized via fluorescein emission, and, because the oxidation of QH 2 at each BPE is strongly dependent on the local pH, via the coupled fluorogenic reaction at the opposite pole of the corresponding BPE digit in the reporter channel. Thus, BPE IDEAs support the coupling of independent redox reactions and the use of fluorescence imaging to explore a diverse set of spatially varying electrochemical phenomena realized in a variety of electrochemical geometries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗