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At least 325 records · Page 18

Multi-fidelity Bayesian neural networks: Algorithms and applications

Here we propose a new class of Bayesian neural networks (BNNs) that can be trained using noisy data of variable fidelity, and we apply them to learn function approximations as well as to solve inverse problems based on partial differential equations (PDEs). These multi-fidelity BNNs consist of three neural networks: The first is a fully connected neural network, which is trained following the maximum a posteriori probability (MAP) method to fit the low-fidelity data; the second is a Bayesian neural network employed to capture the cross-correlation with uncertainty quantification between the low- and high-fidelity data; and the last one is the physics-informed neural network, which encodes the physical laws described by PDEs. For the training of the last two neural networks, we first employ the mean-field variational inference (VI) to maximize the evidence lower bound (ELBO) to obtain informative prior distributions for the hyperparameters in the BNNs, and subsequently we use the Hamiltonian Monte Carlo (HMC) method to estimate accurately the posterior distributions for the corresponding hyperparameters. We demonstrate the accuracy of the present method using synthetic data as well as real measurements. Specifically, we first approximate a one- and four-dimensional function, and then infer the reaction rates in one- and two-dimensional diffusion-reaction systems. Moreover, we infer the sea surface temperature (SST) in the Massachusetts and Cape Cod Bays using satellite images and in-situ measurements. Taken together, our results demonstrate that the present method can capture both linear and nonlinear correlation between the low- and high-fidelity data adaptively, identify unknown parameters in PDEs, and quantify uncertainties in predictions, given a few scattered noisy high-fidelity data. Finally, we demonstrate that we can effectively and efficiently reduce the uncertainties and hence enhance the prediction accuracy with an active learning approach, using as examples a specific one-dimensional function approximation and an inverse PDE problem.

97 MATHEMATICS AND COMPUTING↗

Transients following the loss of detonation confinement

We present a theory for the evolution of a one-dimensional, steady-state detonation reaction zone to a two-dimensional reaction zone, when the explosive experiences a sudden loss of side-on confinement as a boundary of the explosive is impulsively withdrawn. Our focus is on condensed-phase explosives, which we describe as having a constant adiabatic gamma equation of state and an irreversible, state-independent reaction rate. We consider two detonation models: (i) the instantaneous reaction heat release Chapman–Jouguet (CJ)-limit and (ii) the spatially resolved reaction heat-release Zel’dovich–von Neumann–Döring (ZND) model, in the limit where only a small fraction of the energy release is resolved (the SRHR-limit). Two competing rarefaction waves are generated by this loss of confinement: (i) a smooth wave coming off the full length of the withdrawn boundary and (ii) a singular fan spreading out from the point where the detonation shock and the withdrawn boundary meet. For the CJ-limit, in all cases the singular rarefaction fan eventually dominates the competition to control the steady-state behaviour. For the SRHR-limit, the spatially resolved heat release moderates this competition. When the withdrawal speed is fast, the rarefaction fan dominates; when the withdrawal speed is slower, the smooth rarefaction eventually dominates, although the flow features a fan at early times. By examining the mathematical properties of the steady two-dimensional fan-based solution, we set down a mechanism for this transition in behaviours.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Probing growth of metal–organic frameworks with X-ray scattering and vibrational spectroscopy

Nucleation and crystallization arising from liquid to solid phase are involved in a multitude of processes in fields ranging from materials science to biology. Controlling the thermodynamics and kinetics of growth is advantageous to help tune the formation of complex morphologies. In this report, we harness wide-angle X-ray scattering and vibrational spectroscopy to elucidate the mechanism for crystallization and growth of the metal–organic framework Co-MOF-74 within microscopic volumes enclosed in a capillary and an attenuated total reflection microchip reactor. The experiments reveal molecular and structural details of the growth processes, while the results of plane wave density functional calculations allow identification of lattice and linker modes in the formed crystals. Synthesis of the metal–organic framework with microscopic volumes leads to monodisperse and micron-sized crystals, in contrast to those typically observed under bulk reaction conditions. Reduction in the volume of reagents within the microchip reactor was found to accelerate the reaction rate. The coupling of spectroscopy with scattering to probe reactions in microscopic volumes promises to be a useful tool in the synthetic chemist's kit to understand chemical bonding and has potential in designing complex materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helium metastable density determination in the COST reference source by absolutely calibrated optical emission spectroscopy

Helium metastable densities in the COST Reference Microplasma Jet are estimated for a variety of He/N2 admixtures and dissipated powers by applying a collisional-radiative model to absolutely calibrated optical emission spectroscopy measurements. This is accomplished by delineating the excitation mechanisms that result in the N2(C–B) and N2+(B–X) emission bands, the latter of which is strongly coupled to the presence of helium metastables. A number of other plasma parameters are established and discussed for each operating condition including the electron energy distribution function, reduced electric field, rate constants, and electron density. With these parameters, the reaction rates for the primary ionization pathways are also calculated, emphasizing the importance of helium metastables for discharge sustainment. Good agreement with the existing literature is found for most plasma parameters and for helium metastable densities, in particular. A clear [N2]−1 relationship between the nitrogen concentration and density of helium metastables is demonstrated, as has been identified in previous studies in analogous atmospheric pressure plasma jets. This validates the efficacy of this optical technique for determining helium metastable densities and establishes it as a viable, and in many cases, more accessible alternative to other means of quantifying helium metastables in low-temperature plasmas.

Physics↗

Sensitivity of Simulations of Double-detonation Type Ia Supernovae to Integration Methodology

Abstract We study the coupling of hydrodynamics and reactions in simulations of the double-detonation model for Type Ia supernovae. When assessing the convergence of simulations, the focus is usually on spatial resolution; however, the method of coupling the physics together as well as the tolerances used in integrating a reaction network also play an important role. In this paper, we explore how the choices made in both coupling and integrating the reaction portion of a simulation (operator/Strang splitting versus the simplified spectral deferred corrections method we introduced previously) influences the accuracy, efficiency, and nucleosynthesis of simulations of double detonations. We find no need to limit reaction rates or reduce the simulation time step to the reaction timescale. The entire simulation methodology used here is GPU-accelerated and made freely available as part of the Castro simulation code.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Reduction of the neutron imaginary potential off the stability line and its possible impact on neutron capture rates

The effect of the isovector imaginary optical potential has been studied experimentally by using the particle-evaporation technique for the 11 B + 48 Ca reaction with a 21.8 MeV 11 B beam. Spectra of neutron, proton, and α particles emitted from the neutron-rich compound nucleus 59 Mn have been measured and analyzed with traditional optical model potentials with their original parametrizations as well as with adjusted isovector imaginary components. It is shown that the isovector component of the imaginary potential is indispensable in the reproduction of proton and α-particle yields from this reaction and even needs to be enhanced compared with the suggestions of the original model parametrizations. Furthermore, this can lead to important consequences for astrophysical reaction-rate calculations.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Chemical Kinetics of the Autoxidation of Poly(ethylenimine) in CO 2 Sorbents

The oxidative degradation rates of a CO 2 sorbent composed of a mesoporous alumina impregnated with poly- (ethylenimine) (PEI) are measured under systematically varied conditions and a reaction rate law is created. Good agreement is shown between the rate of oxidation obtained via in situ calorimetric heat measurement during oxidative degradation reactions and the loss of CO 2 capture performance presented as amine efficiency (mol CO 2 /mol amine). PEI mass loss and elemental composition are tracked over the course of the reaction and used in conjunction with the oxidation rate measurements to shed insight into the oxidation reaction(s). These data, in combination with measurements of the heat of reaction, suggest a common reaction set across the range of temperatures, oxygen concentrations, and sorbent compositions tested. The data are consistent with the basic autoxidation scheme (BAS), the accepted mechanism of autoxidation of aliphatic polymers. We propose a lumped kinetic model to describe the oxidation reaction set and estimate an activation energy of 105 kJ/mol and an oxygen reaction order of 0.5–0.7 from the data accordingly. Furthermore, these parameters can be incorporated into process cycle models to estimate the material lifetime, a critical uncertainty in the deployment of DAC technologies.

36 MATERIALS SCIENCE↗

Rates of levoglucosanol hydrogenolysis over Brønsted and Lewis acid sites on platinum silica-alumina catalysts synthesized by atomic layer deposition

Nanoscale coatings of AlO x were deposited onto SiO 2 using atomic layer deposition (ALD) to synthesize amorphous silica-alumina (SiAl) catalysts, and these catalysts were investigated for levoglucosanol (Lgol) hydrogenolysis. With decreasing Al 2 O 3 loading, the ratio of Brønsted to Lewis acid sites, measured by NH 3 -TPD and pyridine-FTIR, systematically increases, while the Al coordination, measured by solid state 27 Al NMR, decreases. These structural changes correspond to an increasing mass-normalized rate of Lgol hydrogenolysis. We model the mass-normalized reaction rate as the sum of independent contributions from Brønsted and Lewis sites, showing that Brønsted acid sites on ALD-AlO x /SiO 2 catalysts have a 6-times higher turnover frequency (TOF) than Lewis acid sites on these catalysts. Additionally, Lewis acid sites on ALD-AlO x /SiO 2 catalysts (potentially related to Al(V) species) have a 4-times higher TOF than Lewis acid sites on bulk γ-Al 2 O 3 . The overall mass-normalized reactivity of ALD-AlO x /SiO 2 catalysts is due to Lewis acid sites at the highest Al 2 O 3 loading, while it is predominantly due to Brønsted acid sites at the lowest Al 2 O 3 loadings. In conclusion, this work provides a new approach to synthesize amorphous SiAls with tunable Brønsted/Lewis acid site ratio and reveals differences in the reactivity of Brønsted and Lewis acid sites on these materials.

36 MATERIALS SCIENCE↗

Microwave Synthetic Routes for Shape-Controlled Catalyst Nanoparticles and Nanocomposites

The use of microwave irradiation for the synthesis of inorganic nanomaterials has recently become a widespread area of research that continues to expand in scope and specialization. The growing demand for nanoscale materials with composition and morphology tailored to specific applications requires the development of facile, repeatable, and scalable synthetic routes that offer a high degree of control over the reaction environment. Microwave irradiation provides unique advantages for developing such routes through its direct interaction with active reaction species, which promotes homogeneous heat distribution, increased reaction rates, greater product quality and yield, and use of mild reaction conditions. Many catalytic nanomaterials such as noble metal nanoparticles and intricate nanocomposites have very limited synthetic routes due to their extreme temperature sensitivity and difficulty achieving homogeneous growth. This work presents recent advances in the use of MW irradiation methods to produce high-quality nanoscale composites with controlled size, morphology, and architecture.

59 BASIC BIOLOGICAL SCIENCES↗

Consequences of adsorbate-adsorbate interactions for apparent kinetics of surface catalytic reactions

Lateral adsorbate interactions at catalyst surfaces are known to influence adsorption energies and reaction rates. Lattice-based kinetic Monte Carlo (kMC) simulations are able to capture these influences, but such models are typically parameterized for a specific reaction network and catalyst surface. Here we report kMC simulations to probe the influence of lateral interactions on simulated rates, rate orders, apparent activation energies, and Sabatier plots. We construct a simple, two-step reaction network involving a single adsorbate and rate- limiting diatomic dissociation, employ a generic repulsive lateral interaction model consistent with known adsorbate-adsorbate interactions on metal surfaces, and a rate model consistent with known Brønsted-Evans-Polyani relationships for diatomic dissocations. Furthermore, we juxtapose reaction kinetics over a wide range of reaction conditions and catalyst binding energies, as a function of interaction strength. We find that at a given zero-coverage binding energy and external conditions, adsorbate coverage decreases monotonically with increasing interaction strength, but absolute rates can vary linearly or nonlinearly. Interactions flatten the Sabatier volcano and shift the maximum towards stronger binding. Influences on apparent rate orders and activation energies are modest and are sensitive to interaction-induced adsorbate ordering. Model predictions are sensitive to lattice size effects at high coverages. The results, modelled for a simple reaction system, highlight the generic consequences of lateral interactions and guidance for identifying their signatures in observed kinetics.

kinetic Monte Carlo↗

Kinetics, Products, and Brown Carbon Formation by Aqueous-Phase Reactions of Glycolaldehyde with Atmospheric Amines and Ammonium Sulfate

Glycolaldehyde (GAld) is a C 2 water-soluble aldehyde produced during the atmospheric oxidation of isoprene and many other species and is commonly found in cloudwater. Previous work has established that glycolaldehyde evaporates more readily from drying aerosol droplets containing ammonium sulfate (AS) than does glyoxal, methylglyoxal, or hydroxyacetone, which implies that it does not oligomerize as quickly as these other species. Here, we report NMR measurements of glycolaldehyde’s aqueous-phase reactions with AS, methylamine, and glycine. Reaction rate constants are smaller than those of respective glyoxal and methylglyoxal reactions in the pH range of 3–6. In follow-up cloud chamber experiments, deliquesced glycine and AS seed particles were found to take up glycolaldehyde and methylamine and form brown carbon. At very high relative humidity, these changes were more than 2 orders of magnitude faster than predicted by our bulk liquid NMR kinetics measurements, suggesting that reactions involving surface-active species at crowded air–water interfaces may play an important role. The high-resolution liquid chromatography–electrospray ionization–mass spectrometric analysis of filter extracts of unprocessed AS + GAld seed particles identified sugar-like C 6 and C 12 GAld oligomers, including proposed product 3-deoxyglucosone, with and without modification by reactions with ammonia to diimine and imidazole forms. Chamber exposure to methylamine gas, cloud processing, and simulated sunlight increased the incorporation of both ammonia and methylamine into oligomers. Many C 4 –C 16 imidazole derivatives were detected in an extract of chamber-exposed aerosol along with a predominance of N-derivatized C 6 and C 12 glycolaldehyde oligomers, suggesting that GAld is capable of forming brown carbon SOA.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Submonolayer Is Enough: Switching Reaction Channels on Pt/SiO 2 by Atomic Layer Deposition

The reaction mechanism of CO 2 with H 2 is studied on platinum nanoparticles supported on fumed silica. It is found that platinum nanoparticle size, reaction temperature, and metal oxide promoters play important roles in determining the reaction rate and the mechanism of forming surface carbonyl species. Metal oxide promoters consist of sub-monolayer titanium oxide or aluminum oxide overcoated onto the catalysts by atomic layer deposition (ALD). Furthermore, these alter the CO formation rate, influence the adsorption and desorption behavior, and switch the surface reaction channel from Eley-Rideal to Langmuir-Hinshelwood mechanism due to an enhancement of CO 2 affinity to the metal-metal oxide interface. At the temperatures relevant for catalytic turnover, ALD overcoating significantly increases catalytic activity in CO 2 hydrogenation to CH 4 and CO, while the identity of the oxide overcoat helps control product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Controlling selectivity for dechlorination of poly(vinyl chloride) with (xantphos)RhCl

Reaction of poly(vinyl chloride) (PVC) with 5 equiv. of triethyl silane in THF, in the presence of in situ generated (xantphos)RhCl catalyst, results in partial reduction of PVC via hydrodechlorination to yield poly(vinyl chloride-co-ethylene). Increasing catalyst loading or using N,N-dimethylacetamide (DMA) as a solvent both diminished selectivity for hydrodechlorination, promoting competitive dehydrochlorination reactions. Reaction of PVC with 2 equiv. of sodium formate in THF in the presence of (xantphos)RhCl affords excellent selectivity for hydrodechlorination along with complete PVC dechlorination, yielding polyethylene-like polymers. Higher catalyst loadings were necessary to activate PVC towards reduction in this case. In contrast, reaction of PVC with 1 equiv. of NaH in DMA, in the presence of (xantphos)RhCl, exhibited good selectivity for dehydrochlorination, as well as much higher reaction rates. These results combined shed light on the interplay between critical reaction parameters that control PVC's mode of reactivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

KinCat v.1.0

SAND2024-02099O The software is designed to allow researchers to perform kinetic Monte Carlo (KMC) simulations of catalytic reactions on a 2D lattice. The code is written efficiently to run on a variety of shared memory computing architectures (e.g. GPU, multi-core) and to natively express the full complexity of lateral interactions on reaction rates. The software allows researchers to perform KMC simulations of catalytic reactions on a 2D lattice. It uses parallel shared-memory computing architectures to reduce run-times and allows for simultaneous simulation of multiple independent runs. Sandia National Laboratories is a multimission laboratory managed and operated by National Technology & Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA0003525.

Najm, Habib↗

The Reaction of o-Benzyne with Vinylacetylene: An Unexplored Way to Produce Naphthalene

Herein, the mechanisms and kinetics of the reaction of ortho-benzyne with vinylactylene have been studied by ab initio and density functional CCSD(T)-F12/cc-pVTZ-f12//B3LYP/6-311G(d,p) calculations of the pertinent potential energy surface combined with Rice-Ramsperger-Kassel-Marcus - Master Equation calculations of reaction rate constants at various temperatures and pressures. Under prevailing combustion conditions, the reaction has been shown to predominantly proceed by the biradical acetylenic mechanism initiated by the addition of C4H4 to one of the C atoms of the triple bond in ortho-benzyne by the acetylenic end, with a significant contribution of the concerted addition mechanism. Following the initial reaction steps, an extra six-membered ring is produced and the rearrangement of H atoms in this new ring leads to the formation of naphthalene, which can further dissociate to 1- or 2-naphthyl radicals. The o-C 6 H 4 + C 4 H 4 reaction is highly exothermic, by ~143 kcal/mol to form naphthalene and by 31-32 kcal/mol to produce naphthyl radicals + H, but features relatively high entrance barriers of 9-11 kcal/mol. Although the reaction is rather slow, much slower than the reaction of phenyl radical with vinylacetylene, it forms naphthalene and 1- and 2-naphthyl radicals directly, with their relative yields controlled by the temperature and pressure, and thus represents a viable source of the naphthalene core under conditions where ortho-benzyne and vinylacetylene are available.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis of wafer-scale SWCNT forests with remarkably invariant structural properties in a bulk-diffusion-controlled kinetic regime

Robust synthesis of vertically aligned carbon nanotubes (VACNT) at large scale is required to accelerate deployment of numerous cutting-edge devices to emerging commercial applications. To address this need, this work demonstrates that the structural characteristics of single-walled CNTs (SWCNTs) produced in a growth regime dominated by bulk diffusion of the gaseous carbon precursor are remarkably invariant over a broad range of process conditions (precursor concentration increased up to 30-fold, catalyst substrate area from 1 cm 2 to 180 cm 2 , growth pressure from 20 to 790 mbar, and gas flowrates up to 8-fold). A simple growth kinetics model is derived that accounts for both reactant bulk diffusion and competing byproduct formation in the presence of excess hydrogen, which quantitatively reproduces the experimental data in the entire isothermal parameter space. The model enables critical predictions for process scale-up optimization including a potential 6-fold increase in CNT production rate, a ~90% carbon conversion efficiency in select conditions, and elimination of reaction rate decay observed at high pressures by using a hydrogen-free growth environment. This model-guided opportunity to substantially improve synthesis throughput and efficiency, in conjunction with the remarkably invariant CNT properties, is appealing for reliable VACNT device fabrication at both small and industrial scales.

36 MATERIALS SCIENCE↗

Towards ternary binders involving limestone additions — A review

The review summarises literature to examine the transition from portland limestone cement system to composite ternary binder systems involving limestone. Interest in limestone addition as an ideal component in multicomponent binder systems has surged as evident from the large volume of literature published in the recent past. A ternary blended system, with co-substitution of limestone, has the potential to complement the reaction of the supplementary cementitious materials (SCMs). The direct addition of limestone powder helps to attain higher substitution levels of portland cement clinker, improve early age properties, and supplement SCM's reactivity. However, the dilution of hydrates could hamper the long-term benefits. In this review, the interaction of fine limestone is classified and elaborated under two broad umbrellas: physical and chemical interactions. The physical interactions can manifest in three ways, namely, filler action, shearing action and improved packing, which alters reaction rate and extent at early ages. The chemical interactions also modify the reaction kinetics and phase assemblage due to nucleation of C-S-H on calcite surfaces, preservation of the ettringite phase and formation of carboaluminates. Two different forms of carboaluminate hydrates — hemicarboaluminate and mono-carboaluminate can be present in the hydrate matrix depending on the balance between carbonate ions and aluminates in the pore solution. Several factors such as replacement level, particle size, choice of SCM, its reactivity and reactive aluminates content, sulphate levels, curing temperature, and duration of curing can control the carboaluminate formation, reaction degree of SCMs and chemical interaction from limestone additions. A combination of physical and chemical effects makes fine limestone a potential material for co-substitution with aluminosilicate based SCMs, mainly fly ash, slag, and calcined clay. In this review, the factors affecting limestone-SCM composites are summarised based on a detailed literature survey. The effects of SCM-limestone cement composites on hydration kinetics, reaction chemistry, the reactivity of SCMs, the stability of hydrated phases, and contribution to the physical structure development and macroscopic properties by evaluating hydration and mechanical properties are discussed. The importance of AFm (Al{sub 2}O{sub 3}–Fe{sub 2}O{sub 3}-mono) phases in various deterioration mechanisms in concrete and their influence on performance characteristics in different exposure environment is critically appraised.

36 MATERIALS SCIENCE↗

Cross-Scale Catalyst Modeling Applied to H 2 Storage and Release via Formic Acid

Here, we propose the Systems-to-Atoms (S2A) modeling framework that integrates the kinetics of reaction chemistry and structural configurations across various length scales with the aim of establishing a versatile template for multiscale modeling of reactive flow problems and to predict the operando activity of catalyst materials. The approach encompasses a microkinetic model to analyze surface reactions on individual facets of catalyst nanoparticles coupled with the computation of average surface reaction rates for catalyst nanoparticles of specific size distributions. Macro-homogeneous surface reaction kinetics are derived as a function of catalyst loading and used as input parameters for the continuum-scale reactor model. The cross-scale framework enables the optimization of catalyst utilization through reactor design and operating strategy. To demonstrate the framework, we studied the storage and release of hydrogen from formic acid, a promising liquid organic hydrogen carrier (LOHC), over Pd, Pt, and Cu catalysts. The framework predicts observed trends in formic acid dehydrogenation activity for catalysts with comparable weight loadings and metal particle diameters, demonstrating satisfactory quantitative alignment. Finally, the seamless transmission of parameter uncertainties between scales is also discussed.

08 HYDROGEN↗