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At least 145 records · Page 8

Blowing in the dark matter wind

Abstract Interactions between dark matter and ordinary matter will transfer momentum, and therefore give rise to a force on ordinary matter due to the dark matter ‘wind.’ We show that this force can be maximal in a realistic model of dark matter, meaning that an order-1 fraction of the dark matter momentum incident on a target of ordinary matter is reflected. The model consists of light (m ϕ ≲ eV) scalar dark matter with an effective interaction$$ {\phi}^2\overline{\psi}\psi $$ ϕ 2 ψ ¯ ψ , whereψis an electron or nucleon field. If the coupling is repulsive and sufficiently strong, the fieldϕis excluded from ordinary matter, analogous to the Meissner effect for photons in a superconductor. We show that there is a large region of parameter space that is compatible with existing constraints, where the force is large enough to be detected by existing force probes, such as satellite tests of the equivalence principle and torsion balance experiments. However, shielding of the dark matter by ordinary matter prevents existing experiments from being sensitive to the dark matter force. We show that precise measurements of spacecraft trajectories proposed to test long distance modifications of gravity are sensitive to this force for a wide range of parameters.

Physics↗

Modeling Equilibrium Solid–Liquid Interfaces under Effective Constant Chemical Potential Using Machine Learning Interatomic Potentials

The chemical potential (μ) of species in solution is essential for understanding various chemical processes at interfaces. Molecular dynamics (MD) simulations, constrained by fixed compositions, cannot maintain constant chemical potential with reference to a targeted concentration or chemical potential under nonequilibrium or dynamic conditions, as solute species can migrate to the interface and deplete (or enrich) the bulk due to solute-interface interactions. In this study, we introduce a simple and computationally efficient approach named iterative quasi-constant chemical potential molecular dynamics (iqCμMD) simulation, which helps simulate targeted molar concentrations of species in solution. iqCμMD overcomes the limitations of conventional MD by adjusting the number of species in the solution to reach a target bulk concentration (chemical potential), which allows simulation of the interface under the bulk conditions comparable to experiment. We demonstrate our approach using machine learning interatomic potential (MLIP)-based MD simulations of the Na 2 SO 4,aq –graphene interface, and to show the transferability of our approach, we also perform classical force field-based MD simulations of NaCl aq –air and NaCl aq –graphite interfaces, which produce comparable results to previous CμMD simulations. Our results also show that the iqCμMD approach efficiently achieves the desired bulk ion concentration within two iterations, and by utilizing MLIPs, we can achieve converged results using relatively small-scale simulations compared to previous CμMD simulations. By combining iqCμMD with MLIP-driven simulations, solid–liquid interfaces can be modeled under an effective constant chemical potential with DFT-level accuracy. Here, we show that iqCμMD offers a robust and simple computational framework for constant chemical potential simulations, as its only requirement is to be able to converge interfacial simulations with a measurable bulk region.

Chemical structure↗

On the Interfacial Behavior of Catenated Poly(l-lactide) at the Air–Water Interface

Interfacial properties of polymeric materials are significantly influenced by their architectural structures and spatial features, while such a study of topologically interesting macromolecules is rarely reported. Here, we reported, for the first time, the interfacial behavior of catenated poly(l-lactide) (C-PLA) at the air–water interface and compared it with its linear analogue (L-PLA). The isotherms of surface pressure–area per repeating unit showed significant interfacial behavioral differences between the two polymers with different topologies. Isobaric creep experiments and compression–expansion cycles also showed that C-PLA demonstrated higher stability at the air–water interface. Interestingly, when the films at different surface pressures were transferred via the Langmuir–Blodgett method, successive atomic force microscopy imaging displayed distinct nanomorphologies, in which the surface of C-PLA exhibited nanofibrous structures, while that of the L-PLA revealed a smoother topology with less fiber-like structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Neural network potentials with effective charge separation for non-equilibrium dynamics of ionic solids: a ZnO case study

Developing neural network potentials (NNPs) accurate under non-equilibrium dynamics is challenging, as such systems require extensive sampling beyond equilibrium phases. Here we construct high-fidelity NNPs for zinc oxide (ZnO), a polymorphic ionic solid, using density functional theory (DFT) reference data. To efficiently capture transitional configurations, we combine enhanced-sampling molecular dynamics with empirical potentials, data distillation, and pretraining on short-range atomic energies (A-Train), followed by transfer learning with DFT-relabeled datasets. This hierarchical approach improves transferability across polymorphs and stress states. We further introduce effective charge separation, treating long-range Coulombic terms analytically while short-range residual interactions are learned by the NNP. The optimal effective charges fall in the range 0.5–1.0 q e , consistent with dielectric-screened values derived from formal charges but distinct from Bader estimates. Motivated by this observation, we propose a simple data-driven protocol in which effective charges are optimized by comparing DFT reference energies with explicit Coulomb calculations, without additional NNP training. This strategy improves accuracy and transferability in DFT-level predictions of energies, forces, and stress. Together, these results provide a practical charge-selection framework for robust NNP development in ionic solids, enabling reliable simulation of polymorphic phase transformations and non-equilibrium dynamics.

Chemistry↗

Modeling and Optimal Design of a Desalination System Integrated Between a Glass-Covered Solar Collection Water Chamber and a Heat Dissipating Chimney

Abstract Solar thermal energy is trapped in a glass-covered water chamber/basin to provide the heat for evaporation of brackish water in a novel desalination system. To harvest clean water, a chimney is integrated with the water basin, which draws air into the chamber to be humidified by the vapor and then being ventilated via buoyance force. Uniquely, thermal conductive metal sheet is recommended to make the chimney, which allows the vapor in the humid air condenses easily when flowing up. The condensate at the inner wall of the chimney flows down to be collected as clean water. Mathematical modeling and numerical computation have been carried out to delineate the coupling of the buoyance-force-driven flow with the heat and mass transfer of air and water in the solar collection chamber and the condensation of vapor in the heat-dissipating chimney. The objective of the simulation and optimization of the system is to find the best match of the dimensions of the water chamber with a chimney to maximize the production of clean water and energy efficiency. The model has been used to simulation several cases (of water from 40 °C to 50 °C) with available experimental data from the authors’ previous work, and the agreement was satisfactory. The optimization studies found that there is a maximum air flowrate corresponding to a critical chimney height due to the requirement that the chimney is designated to dissipate heat as much as possible to condense water vapor. With the chimney height greater than the critical height, the airflow rate will have a slight decrease. Nevertheless, higher than a critical height is still needed for a chimney to condense more moisture. Optimized chamber diameters at different chimney heights are provided for reference of optimal system designs.

Engineering↗

Report of the Atmosphere to Electrons Land-Based Mesoscale-to-Microscale Coupling Project (FY2020)

The overall goal of the Mesoscale-to-Microscale Coupling (MMC) project is to improve coupling between mesoscale and microscale simulations via improved guidance and new strategies for setting up simulations and for the development of new tools that can be used across the community. Including the mesoscale forcing is critical to modeling the full energy transfer across scales in the atmosphere. The project-specific objectives include: 1) To apply rigorous verification and validation (V&V) techniques to the new modeling tools that are developed as part of the project to ensure the accuracy of our codes and results and to develop estimates of the relative uncertainty. 2) To improve computational performance of the coupled MMC models through the development of methods that can be used to reduce turbulence spin-up time and hence the size of computational domains. 3) To improve representation of the surface layer in microscale models to enhance simulations of hub-height wind speed. 4) To develop guidance for the community describing the best ways to couple mesoscale and microscale models, including specific spatial scales at which the handoff to the microscale model should occur. 5) To prepare documentation and a suite of software tools that can be used across the community. And 6) To transition MMC research to the offshore environment. Major progress was made in each of these areas during FY20. The land-based portion of the project is reported herein, while the offshore portion will be reported separately. The team continued to advance the MMC tools and methodologies as well as to document their performance in journal papers and conference presentations, although several planned conferences were cancelled due to the COVID-19 pandemic.

54 ENVIRONMENTAL SCIENCES↗

CFD Modeling of Concentration Polarization in High-Performance Flat-Sheet Modules

Membrane-based gas separation is a promising, regeneration-free route for industrial CO₂ capture, but its performance is often limited by concentration polarization (CP). Classical 1-D models neglect CP and thus overpredict fluxes, especially for today’s high-permeance, high-selectivity membranes. Therefore, we built a 3-D CFD model that resolves local species transport, boundary-layer resistance, permeate-side effects, and pressure drop in flat-sheet modules. Using the Concentration Polarization Coefficient (CPC) and the overall Effective Membrane CP Index (EAC), the model quantifies how geometry and operating conditions shape CP intensity. Simulations show CP becomes pronounced for advanced membranes, with feed-channel height emerging as the dominant geometric lever: shrinking the gap mitigates CP but raises pressure drop, forcing a trade-off between mass-transfer enhancement and energy cost. These insights emphasize the need for CFD-level analysis in next-generation module design, where 1-D treatments can severely underestimate required membrane area and misguide scale-up.

carbon capture↗

Radiative Heat Transport and Optical Characterization of High Temperature Molten Salts

The goal of this project was to advance the field of molten fluoride radiative heat transfer (RHT), through optical property measurements, heat transfer loop construction and operation, and computational fluid dynamics simulations. The following outcomes have been accomplished. A comprehensive review has been conducted to compile all available RHT-relevant optical absorption data for molten fluorides. The various measurement methods have also been compiled and critiqued. Thermal emission measurement methods have been refined and documented. A unique thermal emissivity measurement facility has been constructed and used to measure the emissivity of flowing FLiBe-exposed SS316 samples. A slight increase has been observed in the emissivity compared to unexposed SS316. A dual reflectance-emission setup was partially demonstrated for the purpose of molten fluoride absorption measurement. Preliminary infrared edge data for FLiNaK was obtained. A visible near-infrared (NIR) measurement setup has been constructed and will be used to measure absorption of corrosion products in FLiBe. A new multi-band thermal radiation method using blackbody-weighted spectral bands for the absorption-coefficient was deployed to investigate the thermal performance of the UW Natural Circulation FLiBe Loop under various power levels and operating conditions. The results showed an increasing and decreasing trend in the overall heat transfer with optical thickness with a maximum at optical thickness τ D ≈Ο(1). A forced convection FLiBe loop was constructed for the purpose of studying corrosion and thermal hydraulic phenomena. A vertical cantilever pump is used to achieve up to 5 gpm and 5 m/s flow velocity in hot and cold test sections. A methodology has been established for modeling radiative heat transfer (RHT) in molten salt coolants for the purpose of quantifying the contribution of thermal radiation in conditions relevant to FHR or MSR systems. The comparison between the results obtained for forced and mixed convection showed that in the studied ranges of optical thickness, the maximum effect of RHT on overall heat transfer was 60% improvement observed at z/D = 250 for forced convection; whereas for mixed convection, that value was higher at 170% observed at z/D = 30. The highest effect of RHT on the overall energy distribution was observed at τ D ≈3.4. Negligible effect (<20%) was observed above τ D =18 and below τ D ≈0.002. A CFD code-to-code comparison was conducted using COMSOL Multiphysics at UW-Madison and STAR-CCM at MIT, for a forced and mixed convection laminar flow for a grey medium in a vertical heated using both COMSOL Multiphysics at UW-Madison and STAR-CCM at MIT. The relative error was the largest at τ D =40 for the radiative heat flux, bulk temperature, and Nusselt number. On the other hand, the relative error was the least at τ D =0.002 for the conductive heat flux, bulk temperature, and Nusselt number.

Anderson, Mark↗

Direct Evidence for Buffer-Enhanced Proton-Coupled Electron Transfer Generation of a High-Valent Metal-Oxo Complex

Here, the oxidation of metal-aquo and -hydroxo complexes to generate the high-valent metal-oxo species used in oxidative catalysis is often kinetically slow due to sluggish proton transfer between ligated −H 2 O/–OH in the proton-coupled electron transfer (PCET) chemistry. In this research, a ruthenium water oxidation catalyst anchored to a conductive tin-doped indium oxide (ITO) thin film, abbreviated ITO|Ru II –OH 2 , was characterized by spectroscopic and electrochemical methods in acetate or phosphate buffers. The deprotonated intermediate, Ru II –OH, was observed spectroscopically in the PCET half-reaction ITO(e – )|Ru III –OH + H + → ITO|Ru II –OH 2 indicating an underlying stepwise ET-PT mechanism. In contrast, at elevated buffer concentrations, this intermediate was absent, and a 2–4 order of magnitude increase in the proton transfer rate constant was observed. Kinetic data for this PCET reaction measured as a function of the driving force provided the reorganization energy λ = 1.05 eV and was assigned to a concerted electron–proton transfer (EPT) mechanism. In addition, the standard heterogeneous rate constants for two PCET equilibria, Ru III –OH + H + + e – ⇌ Ru II –OH 2 and Ru IV = O + H + + e – ⇌ Ru III –OH were enhanced by these same buffers. Collectively, the data show that the added buffers can enhance the kinetics and thermodynamics for PCET reactions relevant to oxidative catalysis.

Catalysts↗

Electrostatics, Charge Transfer, and the Nature of the Halide–Water Hydrogen Bond

Binary halide–water complexes X – (H 2 O) are examined by means of symmetry-adapted perturbation theory, using charge-constrained promolecular reference densities to extract a meaningful charge-transfer component from the induction energy. As is known, the X – (H 2 O) potential energy surface (for X = F, Cl, Br, or I) is characterized by symmetric left and right hydrogen bonds separated by a C 2v -symmetric saddle point, with a tunneling barrier height that is <2 kcal/mol except in the case of F – (H 2 O). Our analysis demonstrates that the charge-transfer energy is correspondingly small (<2 kcal/mol except for X = F), considerably smaller than the electrostatic interaction energy. Nevertheless, charge transfer plays a crucial role determining the conformational preferences of X – (H 2 O) and provides a driving force for the formation of quasi-linear X··· H–O hydrogen bonds. Here, charge-transfer energies correlate well with measured O–H vibrational redshifts for the halide–water complexes and also for OH – (H 2 O) and NO 2 – (H 2 O), providing some indication of a general mechanism.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of a Systematic and Extensible Force Field for Peptoids (STEPs)

Peptoids (N-substituted glycines) are a class of biomimetic polymers that have attracted significant attention due to their accessible synthesis and enzymatic and thermal stability relative to their naturally occurring counterparts (polypeptides). While these polymers provide the promise of more robust functional materials via hierarchical approaches, they present a new challenge for computational structure prediction for material design. The reliability of calculations hinges on the accuracy of interactions represented in the force field used to model peptoids. For proteins, structure prediction based on sequence and de novo design has made dramatic progress in recent years; however, these models are not readily transferable for peptoids. Current efforts to develop and implement peptoid-specific force fields are spread out, leading to replicated efforts and a fragmented collection of parameterized sidechains. Here, we developed a peptoid-specific force field containing 70 different side chains, using GAFF2 as starting point. The new model is validated based on the generation of Ramachandran-like plots from DFT optimization compared against force field reproduced potential energy and free energy surfaces as well as the reproduction of equilibrium cis/trans values for some residues experimentally known to form helical structures. In conclusion, equilibrium cis/trans distributions (Kct) are estimated for all parameterized residues to identify which residues have an intrinsic propensity for cis or trans states in the monomeric state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

TEAMER: Sandia and CalWave Torque Spring Assessment

Power-take-off (PTO) systems for wave energy converters (WEC) require restoring forces for efficient hydrodynamic as well as mechanical to electric power transfer. Implementation of an effective spring mechanism that can provide a restoring torque on e.g. a rotational, winch type PTO shaft is challenging. SNL in collaboration with CalWave, will use numerical finite element simulations to study application of mechanical torsion springs as a highly efficient restoring force element for CalWave's rotational PTO. Material studies will include common steel as a baseline and potentially advanced materials such as fiber composite materials with different cross-sectional profiles. Test report including description and results of FEA (finite element analysis) models. Excel sheet summarizes which scripts were used for which tables and figures in the report. Part of TEAMER request for technical support (RFTS 1) award to CalWave and Sandia National Lab (SNL).

16 TIDAL AND WAVE POWER↗

Implementation and Validation of Constrained Density Functional Theory Forces in the CP2K Package

Constrained density functional theory (CDFT) is a powerful tool for the prediction of electron transfer parameters in condensed phase simulations at a reasonable computational cost. In this work we present an extension to CDFT in the popular mixed Gaussian/plane wave electronic structure package CP2K, implementing the additional force terms arising from a constraint based on Hirshfeld charge partitioning. This improves upon the existing Becke partitioning scheme, which is prone to give unphysical atomic charges. We verify this implementation for a variety of systems: electron transfer in (H 2 O) 2 + in vacuum, electron tunnelling between oxygen vacancy centers in solid MgO, and electron self-exchange in aqueous Ru 2+ -Ru 3+ . We find good agreement with previous plane-wave CDFT results for the same systems, but at a significantly lower computational cost, and we discuss the general reliability of condensed phase CDFT calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Intermolecular vibrational energy transfer enabled by microcavity strong light–matter coupling

Selective vibrational energy transfer between molecules in the liquid phase, a difficult process hampered by weak intermolecular forces, is achieved through polaritons formed by strong coupling between cavity photon modes and donor and acceptor molecules. Using pump-probe and two-dimensional infrared spectroscopy, we found that the excitation of the upper polariton, which is composed mostly of donors, can efficiently relax to the acceptors within ~5 picoseconds. The energy-transfer efficiency can be further enhanced by increasing the cavity lifetime, suggesting that the energy transfer is a polaritonic process. This vibrational energy-transfer pathway opens doors for applications in remote chemistry, sensing mechanisms, and vibrational polariton condensation.

Science & Technology - Other Topics↗

Lagrangian–Eulerian multidensity topology optimization with the material point method

Abstract In this paper, a hybrid Lagrangian–Eulerian topology optimization (LETO) method is proposed to solve the elastic force equilibrium with the Material Point Method (MPM). LETO transfers density information from freely movable Lagrangian carrier particles to a fixed set of Eulerian quadrature points. This transfer is based on a smooth radial kernel involved in the compliance objective to avoid the artificial checkerboard pattern. The quadrature points act as MPM particles embedded in a lower‐resolution grid and enable a subcell multidensity resolution of intricate structures with a reduced computational cost. A quadrature‐level connectivity graph‐based method is adopted to avoid the artificial checkerboard issues commonly existing in multiresolution topology optimization methods. Numerical experiments are provided to demonstrate the efficacy of the proposed approach.

Li, Yue↗

Electron Transfer Theory Elucidates the Hidden Role Played by Triethylamine and Triethanolamine during Photocatalysis

Triethylamine (TEA) and triethanolamine (TEOA) are renowned, in part, for their ability to reductively quench excited states by outer-sphere electron transfer with vast and still growing applications as sacrificial electron donors for photocatalytic systems. Upon amine oxidation, the resulting TEA •+ and TEOA •+ radical cations undergo proton transfer (or hydrogen atom transfer), resulting in the formation of a chemical reductant that has an α-carbon centered radical adjacent to the nitrogen center (TEA • and TEOA • ). In this contribution, we have electrochemically and spectroscopically characterized a set of electron acceptors which, upon accepting an electron, are a series of photocatalysts, [ReCl(R 1 R 2 -bpy)(CO) 3 ] •– , where R 1 and R 2 are electron-donating and electron-withdrawing groups in the 4,4′- and 5,5′-positions on the bipyridyl ligand. Here, we substantiated the formation of the electron donors, TE(O)A • , by spin trapping electron paramagnetic resonance spectroscopy, where TE(O)A • reacts with 2,4,6-tri-tert-butylnitrosobenzene to generate N-centered and O-centered radical adducts. Having established the chemical behaviors of the electron acceptors and donors individually, the electron transfer rate constants were determined across a 1.43 V range in driving force. The redox potential of TEA • was benchmarked to within ±80 mV on an absolute scale in V vs Fc + /Fc in CH 3 CN by using an empirical rate vs free-energy correlation, electron transfer theory, and density functional theory calculations. The equilibrium potentials for TEA • and TEOA • were determined to be −1.98 V and −1.76 V, respectively. Based on the kinetic and thermochemical analysis presented for TEA • and TEOA • , these transient radicals can be broadly considered strong homogeneous chemical reductants within the wider context of photoredox potentials. Thus, this work clarifies a frequently unnoticed secondary function for these sacrificial electron donors during photocatalysis and rationalizes the possibility of a one-photon/two-electron conversion process that is dependent on the free-energy exchange between TE(O)A • and photocatalysts.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

Effects of polymer grain boundary passivation on organic–inorganic hybrid perovskite field-effect transistors

Despite successful applications of solution-processed organic–inorganic hybrid perovskites (OIHPs) such as archetypical methylammonium lead iodide (MAPI) in high-performance optoelectronic devices including solar cells and light emitting diodes, their application in field-effect transistors (FETs) remains relatively limited due to the unresolved issues caused by ion migration in OIHPs, such as screening of gate electric fields, lowered device on-off ratios and field-effect mobility, and large hysteresis in the FET transfer characteristics. Here, we report improved performances of the MAPI-based FET via a polymer-additive-based grain boundary (GB) passivation approach that suppresses the ion migration. Polycaprolactone (PCL) was incorporated into the MAPI FET as a GB-passivation additive as confirmed by scanning electron and atomic force microscopies. Unlike the typical n-type behavior and large transfer hysteresis in the starting, pristine MAPI FETs, the GB passivation by PCL led to a drastically reduced hysteresis in FET transfer characteristics, while hinting at an ambipolar transport and slight improvement in mobility, indicating a reduced ion migration in the PCL-incorporated MAPI FET. The effect of PCL GB passivation in suppressing ion migration was directly confirmed by the measured, increased activation energy for ion migration in the PCL-incorporated MAPI. Here, the results not only represent the first report of the polymer-additive-based mitigation of the ion migration in the MAPI FET but also suggest potential utilities of the approach for enabling high-performance OIHP FETs and electronic devices in general.

77 NANOSCIENCE AND NANOTECHNOLOGY↗