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At least 181 records · Page 10

Fuel Injection Dynamics and Composition Effects on RDE Performance

Rotating detonation engines (RDEs) provide a promising route to substantially increasing cycle efficiency in stationary gas turbines. Much of this increase relies on the ability to achieve consistent pressure gain within the combustor. In particular, the design of injectors that feed fuel and air into the detonation channel plays a crucial role. Such injectors have to ensure proper mixing of fuel and oxidizer, while minimizing backflow of detonation products into the feed plenums, and reduce susceptibility to the complex wave structures that exist within the combustor. From a practical perspective, such RDEs also need to operate with variable fuel composition. When fuel mixtures with components that possess vastly different oxidation pathways and time-scales are used, there could be additional losses through deflagrative burning instead of detonation-driven heat release. Such sensitivity to the complete flow path is akin to the physics of thermoacoustic instabilities in conventional gas turbines. In this sense, RDEs pose a unique research challenge: the performance of the device relies on the small-scale heat release process, which is highly dependent on the flow interactions within the full-scale system. As a result, canonical flow configurations, instrumented with detailed diagnostics or modeled using high-fidelity tools, but only focus on the small-scale processes will not contain the key system-level interactions. At the same time, macroscopic measurements and models that only capture system-level performance will not provide insight into the key sources of pressure losses. These couplings and sensitivities provide a formidable challenge to both experimental and simulation studies of the effects Thus, a joint experimental/computational program designed specifically to address these challenges was undertaken in this program. The focus of this program was on two key topics: a) the interaction between injector flow and the overall wave dynamics within the combustor, and b) the deflagration/detonation structure in multi-component fuels that are of practical interest. Both topics involve interaction of small-scale heat release processes with the geometry-dependent wave structure. Studies focused on the study of full-scale RDE systems, based on a 6-inch conventional annular geometry. Experimentally RDEs were studied using a combination of diagnostics. A combination of optical diagnostics and aero-thermo-acoustic analysis based on a combination of spectral and mode decomposition analysis was used to identify the dynamics of the detonation wave and other secondary waves that exist in the system. These studies have helped the identification and investigation of injector and detonation dynamics arising from coupling, and how they affect RDE mixing, detonation structure, operability and performance. Performance of RDEs was investigated through thrust stand measurements, which was used to evaluate the effective pressure gain generated by the system through the concept of equivalent available pressure. Optical diagnostics were developed and implemented to investigate the distribution of heat release, across the detonation wave. Novel optical diagnostics of NIR imaging was also developed and applied to investigate the high temperature / high pressure distribution across the detonation wave. In order to complement the experiments, the computational tools were geared to simulate the full experimental setup. GPU-based acceleration of the models and computations were developed to enable rapid simulation of the full system. In addition, the use of adaptive mesh refinement, and unstructured grid formulation, enabled the investigation of realistic geometries studied in the laboratory. The simulations produced a wealth of detail on the structure of the detonation wave under different operating conditions. Emphasis was placed on quantifying mixture pre-burning and the impact on wave propagation and structure.

03 NATURAL GAS↗

High throughput exploration of the oxidation landscape in high entropy alloys

We report high entropy alloys (HEAs) have gained interest for structural applications in extreme environments. With a potentially vast chemical and phase space, there are significant opportunities to discover superior performing alloys. Crucial for most high-temperature applications is understanding and mitigating the oxidation behavior of these chemically complex alloys. Most experimental and computational HEA studies have focused on a limited set of compositions and only a fraction these compositions have been characterized for oxidation. We present a high-throughput framework that utilizes density-functional theory (DFT) in concert with a combined machine-learning model and grand-canonical linear programming for assessing phase stability, phase-fraction, chemical activity and high-temperature survivability of arbitrary HEAs. This framework considers temperature dependent contributions to the Gibbs energy of the competing phases arising from short-range order and vibrational entropy. We demonstrate the effectiveness of the framework by assessing the thermodynamic stability, oxidation behavior, chemical activity, and phase decomposition of body-centered cubic Mo-W-Ta-Ti-Zr refractory HEAs. A total of 51 compositions were analyzed and ranked in order of their survivability based on the Pareto-front analysis. Oxidation was performed at 1373 K on fours samples in air showing the difference in oxidation behavior determined experimentally through scale thickness and their mass changes. The insights on oxidation behavior presented in this work will enable the fast assessment of technologically useful HEAs needed for future structural application in extreme conditions

36 MATERIALS SCIENCE↗

Kinetic Study of Polyvinyl Chloride Pyrolysis with Characterization of Dehydrochlorinated PVC

In this paper, we study the kinetics of polyvinyl chloride (PVC) decomposition using a combination of experimental and computational approaches. Here, we develop a simplified kinetic model that contains only two steps: dehydrochlorination of PVC and further decomposition of the PVC residue. The model is consistent with density functional theory (DFT) calculations and experimental data. Dehydrochlorination is an autocatalytic reaction that starts with a tertiary chloride (Cl) and generates hydrogen chloride (HCl) and benzene as the main products. Benzene and HCl formation rates showed similar trends, indicating that HCl likely catalyzes a homolytic carbon-carbon (C-C) bond cleavage, which gives rise to benzene and an aliphatic fragment. We characterized the structure of dehydrochlorinated PVC (PVC residue) by using thermal gravimetric analysis (TGA), Fourier-transform infrared spectroscopy (FTIR), and nuclear magnetic resonance spectroscopy (NMR). FTIR and NMR results indicate that the PVC residue contains 20% quaternary carbon content, indicating a high concentration of cross-linked molecules. We predict that the most probable structure in the cross-linked centers of the PVC residue is cyclohexadiene, which is supported by DFT calculations, FTIR, and NMR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Nutrient Dynamics in a Coupled Terrestrial Biosphere and Land Model (ELM-FATES-CNP)

We present a representation of nitrogen and phosphorus cycling in the Functionally Assembled Terrestrial Ecosystem Simulator, a demographic vegetation model within the Energy Exascale Earth System land model. This representation is modular, and designed to allow testing of multiple hypothetical approaches for carbon-nutrient coupling in plants. Novel model hypotheses introduced in this work include, (a) the controls on plant acquisition of aqueous mineralized nutrients in the soil and (b) fairly straight forward methods of allocating nutrients to specific plant organs and their losses through live plant turnover as well as litter fluxes generated through plant mortality. This combines the new with pre-existing hypotheses (such as nitrogen fixation and soil decomposition) into a system that can accommodate plant-soil dynamics for a large number of size- and functional-type-resolved plant cohorts within a time-since-disturbance-resolved ecosystem. Root uptake of nutrients is governed by fine root biomass, and plants vary in their fine root biomass allocation in order to balance carbon and nutrient limitations to growth. We test the sensitivity of the model to a wide range of parameter variations and structural representations, and in the context of observations at Barro Colorado Island, Panama. A key model prediction is that plants in the high-light-availability canopy positions allocate more carbon to fine roots than plants in low-light understory environments, given the widely different carbon versus nutrient constraints of these two niches within a given ecosystem. This model provides a basis for exploring carbon-nutrient coupling with vegetation demography within Earth system models.

54 ENVIRONMENTAL SCIENCES↗

Ion Pairing and Redissociaton in Low-Permittivity Electrolytes for Multivalent Battery Applications

Detailed speciation of electrolytes as a function of chemical system and concentration provides the foundation for understanding bulk transport as well as possible decomposition mechanisms. In particular, multivalent electrolytes have shown a strong coupling between anodic stability and solvation structure. Furthermore, solvents that are found to exhibit reasonable stability against alkaline-earth metals generally exhibit low permittivity, which typically increases the complexity of the electrolyte species. To improve our understanding of ionic population and associated transport in these important classes of electrolytes, the speciation of Mg(TFSI)2 in monoglyme and diglyme systems is studied via a multiscale thermodynamic model using first-principles calculations for ion association and molecular dynamics simulations for dielectric properties. The results are then compared to Raman and dielectric relaxation spectroscopies, which independently confirm the modeling insights. We find that the significant presence of free ions in the low-permittivity glymes in the concentration range from 0.02 to 0.6 M is well-explained by the low-permittivity redissociation hypothesis. Here, salt speciation is largely dictated by long-range electrostatics, which includes permittivity increases due to polar contact ion pairs. The present results suggest that other low-permittivity multivalent electrolytes may also reach high conductivities as a result of redissociation.

25 ENERGY STORAGE↗

The phase and turbulent properties of Cattail

ABSTRACT A recent publication discovered one of the largest filamentary neutral hydrogen features dubbed Cattail from high-resolution Five-hundred-meter Aperture Spherical radio Telescope observations that might be a new galactic arm of the Milky Way. We evaluate the turbulent and phase properties of Cattail via the newly developed Velocity Decomposition Algorithm and Force Balancing Model. We discover that if there exists a phase transition, then Cattail is unlikely in the cold neutral media phase. We also show that the Cattail is two disjoint features in caustics space, suggesting that the Cattail has two different turbulent systems. We check the spectra of the individual system separated via VDA to confirm this argument. We do not exclude the existence of smaller scale cold media being embedded within this structure.

79 ASTRONOMY AND ASTROPHYSICS↗

Pyrolysis of bio-derived dioxolane fuels: A ReaxFF molecular dynamics study

Alkyl-substituted 1,3-dioxolanes, including 4,5-dimethyl-2-pentan-3-yl-1,3-dioxolane (Fuel 1), 4,5-dimethyl-2-pentyl-1,3-dioxolane (Fuel 2), and 2-(heptan-3-yl)-4,5-dimethyl-1,3-dioxolane (Fuel 3), have been recently suggested as potential biodiesels. In this paper, we investigate the initial pyrolysis of the alkyl-substituted 1,3-dioxolanes at high temperatures using ReaxFF molecular dynamics (MD) simulations. We analyze the decomposition rate, reaction mechanism, and product distribution in the pyrolysis of the three alkyl 1,3-dioxlanes. The three fuels primarily decompose to 4,5-dimethyl-1,3-dioxolane radical and hydrocarbons derived from the alkyl side-chains. The further decomposition of 4,5-dimethyl-1,3-dioxolane radical primarily leads to 2-C 4 H 8 and CO 2 within a few decomposition steps. The hydrocarbon product distribution is significantly affected by the molecular structure of the alkyl side-chain, which would have a strong influence on the sooting tendency of these fuels. The ReaxFF simulations predict that the order of sooting tendency would be Fuel 3 > Fuel 1 > Fuel 2, which agrees with the measured sooting tendency trend. Based on the pyrolysis mechanism identified by ReaxFF, we propose a new alkyl dioxolane, 4-hexyl-5-methyl-1,3-dioxolane (Fuel 4), which might produce even less soot, by modifying the molecular structure of Fuel 2. Our ReaxFF simulation shows that Fuel 4 produce much less C 4 H 8 , an effective non-aromatic soot precursor, than Fuel 2. Moreover, more carbon atoms are bonded to each oxygen atom in Fuel 4 than Fuel 2, which would help reduce soot yield by removing more carbon atoms from the soot-producing pool of species. The major decomposition pathways identified in this work can be used to develop chemical kinetic models for 1,3-dioxolane based compounds, as biodiesel components, applicable to combustion engine simulations. We also demonstrate that the chemical kinetic insight offered by ReaxFF simulations can be used to design new fuel molecules with more desired properties.

09 BIOMASS FUELS↗

Testing the thermal Sunyaev-Zel’dovich power spectrum of a halo model using hydrodynamical simulations

Statistical properties of large-scale cosmological structures serve as powerful tools for constraining the cosmological properties of our Universe. Tracing the gas pressure, the thermal Sunyaev-Zel’dovich (tSZ) effect is a biased probe of mass distribution and, hence, can be used to test the physics of feedback or cosmological models. Therefore, it is crucial to develop robust modelling of hot gas pressure for applications to tSZ surveys. Since gas collapses into bound structures, it is expected that most of the tSZ signal is within halos produced by cosmic accretion shocks. Hence, simple empirical halo models can be used to predict the tSZ power spectra. In this study, we employed the HMx halo model to compare the tSZ power spectra with those of several hydrodynamical simulations: the Horizon suite and the Magneticum simulation. We examine various contributions to the tSZ power spectrum across different redshifts, including the one- and two-halo term decomposition, the amount of bound gas, the importance of different masses, and the electron pressure profiles. Our comparison of the tSZ power spectrum reveals discrepancies between the halo model and cosmological simulations that increase with redshift. We find a 20% to 50% difference between the measured and predicted tSZ angular power spectrum over the multipole range ℓ = 10 3 − 10 4 . Our analysis reveals that these differences are driven by the excess of power in the predicted two-halo term at low k and in the one-halo term at high k . At higher redshifts ( z ∼ 3), simulations indicate that more power comes from outside the virial radius than from inside, suggesting a limitation in the applicability of the halo model. We also observe differences in the pressure profiles, despite the fair level of agreement on the tSZ power spectrum at low redshift with the default calibration of the halo model. In conclusion, our study suggests that the properties of the halo model need to be carefully controlled against real or mock data to be proven useful for cosmological purposes.

Ayçoberry, Emma (ORCID:0000000292351195)↗

A theoretical kinetic study of ĊH 3 + ṄH 2 : From electronic structure to NH 3 /CH 4 combustion modelling implications

Carbon–nitrogen interaction reactions play an important role in governing the reactivity of ammonia blended fuels. However, there remains uncertainties regarding their detailed reaction pathways and rate constants, hampering the development of high-fidelity chemical kinetic models. In this study, the kinetics of ĊH 3 + ṄH 2 , a key C–N interaction reaction in ammonia/methane blend combustion have been investigated. The potential energy surface has been explored using the high-level ANL0F method, yielding highly accurate stationary point energies that agree with ATcT values within 0.1 kcal mol –1 . Variable reaction coordinate transition state theory is used to treat the barrierless association and decomposition reaction channels, based on directly sampled radical-radical interaction energies at the CASPT2-F12(2e,2o)/cc-pVTZ-F12 level of theory. The minimum transitional mode numbers of states obtained are then coupled with the RRKM/master equation to calculate temperature- and pressure-dependent rate constants. Our a priori calculations capture available experimental measurements from the literature very well. The calculated rate constants have been incorporated into an NH 3 /CH 4 chemical kinetic model currently under development at the University of Galway. The effect of the updated kinetic data for ĊH 3 + ṄH 2 on model predicted NH 3 /CH 4 fuel reactivity is elucidated.

ab initio↗

Real Time Observation of Lithium Insertion into Pre-Cycled Conversion-Type Materials

Conversion-type electrode materials for lithium-ion batteries experience significant structural changes during the first discharge–charge cycle, where a single particle is taken apart into a number of nanoparticles. This structural evolution may affect the following lithium insertion reactions; however, how lithiation occurs in pre-cycled electrode materials is elusive. In this work, in situ transmission electron microscopy was employed to see the lithium-induced structural and chemical evolutions in pre-cycled nickel oxide as a model system. The introduction of lithium ions induced the evolution of metallic nickel, with volume expansion as a result of a conversion reaction. After pre-cycling, the phase evolutions occurred in two separate areas almost at the same time. This is different from the first lithiation, where the phase change takes place successively, with a boundary dividing the reacted and unreacted areas. Structural changes were restricted at the areas having large amount of fluorine, implying the residuals from the decomposition of electrolytes may have hindered the electrochemical reactions. This work provides insights into phase and chemical evolutions in pre-cycled conversion-type materials, which govern electrochemical properties during operation.

25 ENERGY STORAGE↗

Effect of interfacial structures on phonon transport across atomically precise Si/Al heterojunctions

Phonons are important carriers of energy and information in many cryogenic devices used for quantum information science and in fundamental physics experiments such as dark matter detectors. In these systems phonon behavior can be dominated by interfaces, hence there is increasing demand for a more detailed understanding of interfacial phonon transport in relevant material systems. Previous studies have focused on understanding thermal transport over the entire phonon spectrum at and above room temperature. At ultra-low temperatures, however, knowledge is missing regarding athermal phonon behavior due to the challenge in modeling the extreme conditions in micro-scale, heterogeneous cryogenic systems, as well as extracting single-phonon information from a large ensemble. In this work, we delineate interfacial phonon transport using a combination of classical molecular dynamics (MD) and phonon wave packet simulations, to illustrate the consistency and differences between the ensemble- and single-phonon dynamics. We consider three single-crystal Si surface reconstructions --- (1×1), (v3×v3) and (7×7) --- and model both experimentally observed Si(1×1)/Al interfaces and hypothesized Si(v3×v3)/Al and Si(7×7)/Al interfaces. The overall interfacial thermal conductance calculated from non-equilibrium MD shows that for the Si(1×1)/Al system, the presence of Al twin grain boundaries can hinder phonon transport and reduce thermal conductance by 2--12% relative to single-crystal Al; whereas the Si (v3×v3) and (7×7) reconstructions can enhance it by 6--19%. Normal mode decomposition reveals that both the increase and decrease in conductance are related to inelastic phonon scattering. Single-phonon wave packet simulations show results consistent with NEMD, while further suggesting that phonon polarization conversion is significant even when elastic transmission dominates, and that the interfacial structures have anisotropic impacts on atomic vibrations along different lattice directions. Our findings suggest alternative perspectives in achieving selective phonon transport through controlling interfacial structures of materials with atomically-precise fabrication techniques, and that the phonon wave packet formalism is a potentially powerful method for developing a detailed understanding of non-equilibrium phenomena in the low-temperature limit.

Lu, Zexi↗

Identifying native point defect configurations in α-alumina

Intimately intertwined atomic and electronic structures of point defects govern diffusion-limited corrosion and underpin the operation of optoelectronic devices. For some materials, complex energy landscapes containing metastable defect configurations challenge first-principles modeling efforts. Here, we thoroughly reevaluate native point defect geometries for the illustrative case of α-Al 2 O 3 by comparing three methods for sampling candidate geometries in density functional theory calculations: displacing atoms near a naively placed defect, initializing interstitials at high-symmetry points of a Voronoi decomposition, and Bayesian optimization. We find symmetry-breaking distortions for oxygen vacancies in some charge states, and we identify several distinct oxygen split-interstitial geometries that help explain literature discrepancies involving this defect. We also report a surprising and, to our knowledge, previously unknown trigonal geometry favored by aluminum interstitials in some charge states. Importantly, these new configurations may have transformative impacts on our understanding of defect migration pathways in aluminum-oxide scales protecting metal alloys from corrosion. Overall, the Voronoi scheme appears most effective for sampling candidate interstitial sites because it always succeeded in finding the lowest-energy geometry identified in this study, although no approach found every metastable configuration. Finally, we show that the position of defect levels within the band gap can depend strongly on the defect geometry, underscoring the need to conduct careful searches for ground-state geometries in defect calculations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Detection of Synchrophasor False Data Injection Attack using Feature Interactive Network

The synchrophasor data recorded by Phasor Measurement Units (PMUs) plays an increasingly critical role in the regulation and situational awareness of power systems. However, the widely installed PMUs are vulnerable to multiple malicious attacks from cyber hackers during data transmission and storage. To address this problem, a Modified Ensemble Empirical Mode Decomposition (MEEMD) is proposed first to extract the intrinsic mode functions of each Synchrophasor Data Attacks (SDA). The frequency-based adaptive screening criterion embedded in MEEMD is used to eliminate the false intrinsic mode functions. Next, a Multivariate Convolutional Neural Network (MCNN) is proposed to identify multiple SDA by utilizing the extracted intrinsic mode functions and original SDA as input vectors. A fusion block as the main structure of MCNN is also leveraged to increase the diversity of features and compress the model parameters. Integrating MEEMD and MCNN, a framework with automatic feature extraction and multi-source information fusion capability, referred to as Feature Interactive Network (FIN), is proposed to detect multiple SDA. Based on the proposed FIN framework, six types of SDA are explored for the first time using actual synchrophasor data in FNET/Grideye that was collected from different locations in the U.S. Eastern Interconnection. Finally, a large quantity of experiments with different attack strengths are used to evaluate the adaptability and classification performance of the proposed FIN.

24 POWER TRANSMISSION AND DISTRIBUTION↗

Analysis of degradation products in thermally treated TATB

Delineating the chemical composition of TATB (1,3,5-triamino-2,4,6-trinitrobenzene) residues produced from the exposure to abnormal thermal environments should lead to a better understanding of the decomposition paths. Identifying and quantifying each compound in thermally produced residues, monitors which compounds are degrading or forming along the decomposition route, as well as providing input for the kinetic models of those pathways. Here, in this paper, we report the methodology of isolating, identifying, and where possible, quantifying soluble compounds present in solid residues of thermally treated TATB (330 °C for tens of minutes). Samples were extracted with DMSO, separated using chromatography, and quantified using their absorption at 354 nm. Identification of unknown compounds was accomplished using high resolution mass spectrometry. TATB, F1 (diamino-dinitro-benzofurazan), HO-TATB (2,4,6-triamino-1-hydroxyl-3,5-dinitrobenzene), and T4A (1-chloro-3,5-dinitro-2,4,6-triaminobenzene) were trace compounds detected in the unreacted TATB. Ten more compounds that formed in the residues were structurally identified including F2 (amino-nitro-difurazan). Several more compounds were observed but not completely identified. We propose possible structures for the unknowns. Of the compounds formed, F1 was the most abundant compound reaching 4.5 % by weight of the degraded solid sample. Other degradation compounds were estimated to sum to trace levels, well below 1 %. Most compounds were new, having not been detected and identified in previous studies of production grade and thermally aged TATB. Many compounds only reached detectable concentrations after several min of thermal exposure.

36 MATERIALS SCIENCE↗

Reduced order models for thermal radiative transfer problems based on moment equations and data-driven approximations of the Eddington tensor

Here a new group of structure and asymptotic preserving reduced-order models (ROMs) for multidimensional nonlinear thermal radiative transfer (TRT) problems is presented. They are formulated by means of the nonlinear projective approach and data compression techniques. The nonlinear projection is applied to the Boltzmann transport equation (BTE) to derive a hierarchy of low-order moment equations. Approximation of the Eddington tensor that provides exact closure for the system of moment equations is found with projection-based data-driven methodologies. These include the (i) proper orthogonal decomposition (POD), (ii) dynamic mode decomposition (DMD) and (iii) a variant of the DMD. A parameterization is derived for this ROM for the temperature of radiation incoming to the problem domain (the radiation drive temperature). This parameterization is informed from results of a dimensionless study of the TRT problem. Analysis of the ROMs is performed on the classical Fleck-Cummings TRT multigroup test problem in 2D geometry with a radiation-driven Marshak wave. Numerical results are presented to demonstrate the performance of these ROMs for the simulation of evolving radiation and heat waves. Results show these models to be sufficiently accurate for practical computations with rather low-rank representations of the Eddington tensor. As the rank of the approximation is increased, the errors of solutions generated by the ROMs gradually decreases.

42 ENGINEERING↗

Metal oxide candidates for thermochemical water splitting obtained with a generative diffusion model

Generative diffusion models (DMs) for inorganic crystalline materials are being actively investigated for their potential to expand the chemical and structural design spaces for known functional materials. Generative candidates are particularly useful for applications where few functional, let alone commercially viable, materials currently exist, such as metal oxides for thermochemical water-splitting, which have strict requirements for defect thermodynamics and host stability. Here, we critically examine generated metal oxides from the M ATTER G EN DM conditioned on select chemical systems for thermochemical water splitting applications. Perhaps most notably, we find that M ATTER G EN predicts a novel, thermodynamically stable, quinary metal oxide, Ba 2 SrInFeO 6 , although this compound represents an ordered and layered substitution within the same A 3 B 2 O 6 structural prototype as its two ternary end members. Detailed density functional theory calculations and spin configuration sampling for this material and its possible decomposition products—beyond what existed in M ATTER G EN training data—are required to quantitatively validate hull energy predictions and conclusions of stability. Furthermore, the material exhibits oxygen defect formation energies appropriate for thermochemical water splitting, warranting targeted investigation in an experimental validation campaign, along with other future M ATTER G EN candidates in this application space.

36 MATERIALS SCIENCE↗

Graph-Based Modeling and Decomposition of Hierarchical Optimization Problems

We present a graph-theoretic modeling approach for hierarchical optimization that leverages the OptiGraph abstraction implemented in the Julia package Plasmo.jl. We show that the abstraction is flexible and can effectively capture complex hierarchical connectivity that arises from decision-making over multiple spatial and temporal scales (e.g., integration of planning, scheduling, and operations in manufacturing and infrastructures). We also show that the graph abstraction facilitates the conceptualization and implementation of decomposition and approximation schemes. Specifically, we propose a graph-based Benders decomposition (gBD) framework that enables the exploitation of hierarchical (nested) structures and that uses graph aggregation/partitioning procedures to discover such structures. In addition, we provide a Julia implementation of gBD, which we call PlasmoBenders.jl. We illustrate the capabilities using examples arising in the context of energy and power systems.

97 MATHEMATICS AND COMPUTING↗

On the prediction of pressure effects for the combination kinetics of two alkyl radicals with the geometric mean rule

Here, alkyl combination reactions, along with their reverse alkane unimolecular decomposition reactions, are widely present in pyrolysis and combustion systems. These reactions occur mainly at temperatures at which their rate coefficients depend on pressure, and only a few studies have explored this dependence for large size alkyls. The accurate calculation of these kinetic data is limited by the size of the alkyl fragments involved, since the theoretical methods used are computationally expensive. Therefore, little reliable data is available for the modeling of real fuels alkane decomposition kinetics. In this paper, we propose an alternative approach that allows an accurate estimation of pressure-dependent kinetic rates for the combination of long-chain alkyl radicals, based on tabulated reaction models. The rates of combination of linear alkyls radicals forming ethane to pentane were calculated using the CASPT2-F12/cc-pVDZ-F12 level within VRC-TST theory combined with master-equation simulations. The computed high-pressure limit rate coefficients showed that n-propyl could be a minimum-size representative structure for larger n-alkyl chain, but this approach fails to capture the pressure dependence of the reaction that remains size-dependent for larger alkyls. The Geometric Mean Rule (GMR), a simple rule that links the self and cross-reactions of three alkyl radicals, is used to address this issue. Our theoretical calculations show for the first time that the GMR applies not only at the high-pressure limit, but also for every pressure explored. The GMR is shown to be accurate, with a maximum 22 % deviation in the falloff region for the estimation of rates for small alkyl combinations. Using this method, we propose a tabulated reaction rate rule for the combination of alkyl radicals up to C5+C5. The use of computed rate coefficients with the GMR approximation opens ways to develop pressure-dependent reaction rate rules for large n-alkyl combinations, based on accurate and computationally expensive theoretical calculations on smaller alkyl fragments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗