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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 343 records · Page 19
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Computational approaches for three-nucleon systems

Highlights: • Pedagogical review on the computational aspects of the three-nucleon system. • Detailed numerical steps for solving the three-body problem. • Three-nucleon binding and scattering for two different separable potentials. • Triton binding with partial-wave projected chiral potentials. We revisit the three-nucleon system with two kinds of nucleon–nucleon interactions: separable potentials and chiral forces, showing the computational aspects in detail. We start with S-wave separable potentials for which there are simplified forms for the Faddeev equations describing the scattering and binding of three nucleons. We then discuss the partial-wave projected case with a chiral potential considering only one channel so that the computational details can be clearly shown.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2021

Simulation-based Performance Evaluation of Model Predictive Control for Building Energy Systems

The performance of model predictive control (MPC) can be significantly affected by different choices of controller parameters such as the time intervals for model discretization and control sampling. Due to the lack of a systematic understanding on how these parameters affect control performance, they are usually selected arbitrarily in practice.In this paper, the combined impacts of selected time intervals for model discretization and control sampling on the performance of MPC are comprehensively investigated for the first time through detailed simulations. Specifically, a typical MPC strategy is first designed to improve building operations based on a reduced-order model of building dynamics. Then, the performance of the designed MPC is evaluated against different choices of time intervals for model discretization and control sampling on a simulated office building. The detailed simulation results reveal that the time interval for model discretization has a much greater influence on the performance of MPC than the time interval for control sampling. Although the time interval for control sampling usually receives more attentions in practice, it turns out that the time interval for model discretization affects the prediction performance, cost saving, and computation time simultaneously and more significantly. Therefore, the simulation-based performance evaluation presented here sheds light on the impacts of different time intervals and facilitates their selection for practical applications of MPC to building operations

Huang, Sen↗
DOE OSTI2023

The interactive indoor-outdoor building energy modeling for enhancing the predictions of urban microclimates and building energy demands

There is a lack of an urban building energy modeling framework that considers the influence of surrounding buildings and local urban climate on building thermal performance. This can lead to inaccurate results since the thermal performance of individual buildings is heavily influenced by their surrounding built and climatic environment. This study establishes an interactive indoor-outdoor building energy modeling method to enhance the predictions of urban microclimates and building energy demands by coupling an urban physics model with a physics-based building energy model. Validation of the interactive coupling scheme uses field measurement datasets. Parametric simulation and analysis are conducted to understand the influence of the roof-to-canyon width ratio, canyon orientation, and ground vegetation fraction on canyon temperature, building energy consumption, and energy demand. Furthermore, the impacts of building energy model complexity (e.g., detailed vs. simplified building models) and coupling approaches on canyon temperature and building energy profiles are demonstrated using two case study buildings. In comparison with the one-way coupling approach, cooling energy consumption predicted with the dynamic two-way coupling approach varies by 3.5% and 0.5% for the detailed medium office building model and high-rise building model, respectively, and peak cooling demand varies by 8.4% and 7.0% for the detailed medium office building model and high-rise building model, respectively. Here this study also suggests that adopting a complex two-way coupling approach with environmental data exchange at various elevations is necessary for modeling tall buildings at the urban scale.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2020

Effects of fuel composition and octane sensitivity on polycyclic aromatic hydrocarbon and soot emissions of gasoline–ethanol blend surrogates

The sooting propensity of a fuel is closely coupled with the fuel composition and chemistry. A detailed understanding of their effects is, therefore, needed to develop next-generation fuels which can minimize particulate emissions. With this overarching goal, the present work numerically investigates the effects of fuel composition and octane sensitivity (S) on polycyclic aromatic hydrocarbons (PAH) and soot emissions, for four-component gasoline-ethanol blend surrogates comprising isooctane, n-heptane, toluene, and ethanol. A partially-premixed counterflow flame is chosen as the canonical configuration for this study and simulations are performed using CHEMKIN-Pro-employing a kinetic mechanism developed by Park et al. (2017). In addition, a, detailed soot model based on the sectional method is used to capture the spatial characteristics of soot emissions. The kinetic mechanism and soot model are validated using available experimental data for various targets. A total of 86 TPRF-E mixtures, spanning a wide range of concentration of each component, and a wide range of S are analyzed. The effect of each non-paraffinic fuel component on the resultant PAH and soot emissions is investigated. PAH and soot emissions are found to vary significantly depending upon the blend composition. Additionally, based on the parametric sweeps, a regression analysis is carried out to identify global parameters that govern the formation of PAHs and soot. The analysis shows that both toluene content and S have a prominent effect on the formation of PAHs and soot, with toluene content having a stronger impact. Moreover, larger PAHs have higher dependency on toluene content and S. Furthermore, a detailed analysis is carried out to understand the physical and chemical phenomena associated with the observed trends of PAH and soot emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Computational diagnostics and characterization of combustion recession in diesel sprays

While low-temperature combustion (LTC) strategies have been found to mitigate nitrogen oxides and particulate matter emissions in diesel engines, studies have also associated LTC with an increase in unburnt hydrocarbons. With more recent studies on diesel after end-of-injection (AEOI), combustion recession is identified as a phenomenon where at near nozzle region, high-temperature ignition (HTI) combustion can propagate back to the nozzle tip consuming the unburnt hydrocarbons AEOI. Current literature has suggested that combustion recession is controlled by auto-ignition. However, high-fidelity simulations and detailed analysis of such a mechanism are missing. In this study, comprehensive Large Eddy Simulations of a reacting spray at “Spray A” conditions are performed, where detailed analysis of combustion recession concerning flame morphology and propagation modes are included. In particular, this study demonstrated for the first time that while combustion recession is mainly auto-ignition dominated (consistent with the literature), a cool flame was found to deflagrate towards the richer regions of the mixture, promoting mixing and increasing the mixture temperature. This leads to HTI kernels, which then grow and develop as deflagrative waves, therefore sustaining the combustion recession process. The study also detailed the extinction mechanism of combustion: the entrainment wave will overlean the near-nozzle mixtures, rendering it unable to support HTI, which leads to the extinction of the upstream flame AEOI in lower reactivity mixtures. Combustion recession is also observed to be contingent on the chemical and diffusion processes, even at low scalar dissipation rates. Finally, a new criterion for combustion recession based on chemical explosive mode is proposed and validated with previous combustion recession index to quantify the extent of HTI in near-nozzle mixtures AEOI. The newly developed metric combined with a previous experimentally-based metric can provide simple but valuable measurements of the degree and propensity of the upstream flame AEOI.

CEMA↗
DOE OSTI2022

Quantifying transport and electrocatalytic reaction processes in a gastight rotating cylinder electrode reactor via integration of Computational Fluid Dynamics modeling and experiments

Understanding the complexity of the multiple processes of mass, momentum, charge, and heat transport, and how these affect reaction kinetics at the electrode/electrolyte interface is one of the major challenges in the field of energy and catalysis. The rapid and rational scale-up of electrocatalytic systems to industrial scales require a detailed understanding of nonlinear transport-reaction processes, accessible only through the building of multi-physics models that capture with high fidelity the complexity of real-world devices. The gastight rotating cylinder electrode (RCE) reactor is a promising lab-scale tool that can decouple transport from intrinsic kinetics to generate data for first-principle models useful in the design of industrial, electrochemical reactors. Computational Fluid Dynamics (CFD) studies have previously been used to investigate the bulk flow in RCE reactors for simple corrosion and electroplating processes. However, the quantification of changes in local concentration within the viscous layer where catalysis takes place requires capturing the correct flow conditions inside the hydrodynamic boundary layer near the surface of the electrode. Further, this requires simulations with spatial resolution in the nm and μm scale and temporal resolutions between ms and s scales that are similar to the timescales for reactions on the electrode surface. In this study, experimental electrocatalysis is combined with CFD modeling to elucidate and parameterize the hydrodynamics in a gastight RCE reactor. CFD simulations of the electrochemical ferricyanide reduction reaction under mass transport limited conditions are used to evaluate the validity of the CFD model parameters by comparing calculated dimensionless mass transport descriptors to dimensionless correlations obtained experimentally. Justifications for assumptions and details of the simulation methods used in this study are presented to provide a detailed understanding of the effect that each model parameter has on the ability to accurately simulate electrocatalysis in RCE systems. The simulation methodology reported here is a first step towards the development of multi-scale models for the study of transport dependent electrocatalytic processes, such as the electrochemical transformation of CO 2 to fuels and chemicals.

42 ENGINEERING↗
DOE OSTI2026

Conditional distribution estimation of building characteristics with diffusion models for urban energy modeling

Understanding current energy consumption behavior in communities is critical for informing future energy use decisions and enabling efficient energy management. Urban energy models, which are used to simulate these energy use patterns, require large datasets with detailed building characteristics for accurate outcomes. However, such detailed characteristics at the individual building level are often unknown and costly to acquire, or unavailable. Through this work, we propose using a generative modeling approach to generate realistic building attributes to fill in the data gaps and finally provide complete characteristics as inputs to energy models. Our model learns complex, building-level patterns from training on a large-scale residential building stock model containing 2.2 million buildings. We employ a tabular diffusion-based framework that is designed to handle heterogeneous (discrete and continuous) features in tabular building data, such as occupancy, floor area, heating, cooling, and other equipment details. We develop a capability for conditional diffusion, enabling the imputation of missing building characteristics conditioned on known attributes. We conduct a comprehensive validation of our conditional diffusion model, firstly by comparing the generated conditional distributions against the underlying data distribution, and secondly, by performing a case study for a Baltimore residential region, showing the practical utility of our approach. Our work is one of the first to demonstrate the potential of generative modeling to accelerate building energy modeling workflows.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗
DOE OSTI2022

Model-based predictive control of multi-zone commercial building with a lumped building modelling approach

Here this study investigates the applicability of a lumped building modeling approach to model-based predictive control (MPC) to alleviate the complex modeling process of the grey-box multi-zone building model. Based on experimental data, two building models were estimated in this study. The detailed model as a reference case and a lumped model were estimated with decentralized and conventional approaches, respectively. Then, simulations were performed with two boundary conditions, including the comfort bound and electricity cost structure. The performances of the MPC with the detailed and lumped models were analyzed compared to the feedback control. More savings was achieved with a larger comfort bound and more aggressive electricity cost structure. The savings potential of the proposed lumped model approach was not as high as that of the detailed model. However, the proposed method yields good control performance, whose savings was approximately 8.6% over that of feedback control. These results suggest that the proposed method can be used to facilitate MPC implementation in multi-zone building applications.

42 ENGINEERING↗
DOE OSTI2021

Numerical analysis of particle dispersion and deposition in coal combustion using large-eddy simulation

High-fidelity modeling provides a useful approach to investigate the particle dispersion and deposition mechanism in pulverized coal combustion. To be able to analyze these detailed mechanisms, this work couples detailed multiphysics models for poly-dispersed turbulent, particle-laden flow, particle and gas phase reaction chemistry, convective, conductive and radiative heat transfer, ash formation and deposition with a Large-Eddy Simulation (LES) approach to numerically simulate coal combustion in a downfired self-sustained oxy-fuel combustor (OFC). It is necessary to explicitly capture all but the highest frequency dynamics of the turbulence and its coupling with each of the other physical phenomena using LES. Effects of subgrid-scale unresolved turbulence on the particle motions are also analyzed by a novel Stokes number analysis. Due to the inherent relation ship between coal combustion and ash deposition, this study integrates the improved ash deposition model into the numerical simulation. Overall simulation results are compared with experimentally measured data from the OFC. The simulation and measured data for the averaged gas temperature and deposition rates agree with 5% and 28%. This study shows that high-fidelity LES coupled with other detailed multiphysics models running on a exascale computing facility can provide a good representation of complex coal combustion and deposition in a laboratory-scale furnace.

multiphysics model↗
DOE OSTI2023

Mechanisms of dissolution from gibbsite step edges elucidated by ab initio molecular dynamics with enhanced sampling

Surface reactions underpin our collective understanding of mineral dissolution. This impacts a range of predictive geochemical models (for weathering, the fate and transport of metals) as well as industrial utilization of minerals. Yet atomistic details are rarely known due to the complex mineral/fluid interfacial environment. There is significant need to understand the mechanistic details of dissolution reactions and how they depend on surface morphology and solution conditions. This work utilizes surface pit models in conjunction with changes to solution composition that mimic pH to explore surface detachment of aluminate from gibbsite, which is a primary source of Al in soils and within the industrial processing of aluminum. Ab initio molecular dynamics simulations with enhanced sampling has been used to explore the detailed process of the detachment, the results of which indicate two potential pathways that are differentiated based upon the extent of water hydration. Here, the heights of the energy barriers depend upon the local morphology which influence the number of bridges (quasi-)simultaneously broken (1 or 2) or the Al-O coordination of the neighboring aluminum atoms (5 or 6) at the armchair edge. pH effects are significant, with a nearly 50% reduction in barrier height under alkaline conditions that are relevant to geothermal fluids and Al extraction from minerals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

A product data network to enable faster, easier, and better planning of building envelopes

The building envelopes contributes significantly to the energy-efficiency of the building. Building performance simulation has made it possible to compare façade technologies regarding energy demand, daylighting, thermal and visual comfort in detail. Planners, such as architects and engineers, need experience to find product data with the right quality and level of detail, and to process the data to fit the calculation and the application. In the available time, planners can compare only a limited number of products, which means that better solutions could go unnoticed. This paper presents a new concept for making product data easily accessible for building façade planning. The concept consists of a network of databases for the efficient exchange and use of optical and calorimetric data of glazing units, shading devices, and combinations of both. The paper presents the research questions, an analysis of the current challenges, six design goals for the product data network and its implementation together with a discussion. Many product data sources can be connected to many planning software applications via the specified application programming interface. When planning software connects to the product data network, the planning of building envelopes can be much faster because planners do not need to spend so much time to search and process product data manually. The planning of building envelopes can also become much easier, especially for planners with limited experience. They do not need to understand all the details about which data fits which calculation if the software company implements this. The planning of building envelopes can become much more reliable when software companies validate their use of the product data network, because the current manual process is prone to errors. The planning of building envelopes can also improve because more products can be compared in the available time, allowing better solutions to be found.

Maurer, Christoph↗
DOE OSTI2022

Statistical characterization of twin transmission across grain boundaries in magnesium

Here, a detailed statistical analysis of twin transmission (TT) across grain boundaries is performed in rolled, commercial purity magnesium compressed along the rolling direction. EBSD images are acquired from two different cuts: a section containing the rolling (RD) and normal (ND) directions; and a section at 35° to the ND which contains transverse direction (TD). An automated twinning analysis software, METIS, is used to obtain the statistical correlations between deformation twins and other microstructural features by analyzing EBSD microstructures comprising thousands of grains and twins. This detailed statistical analysis reveals that the TT propensity is sensitive to the grain boundary (GB) misorientation angle but not to the GB misorientation axis. Specifically, TT propensity decreases with increasing GB misorientation angle; however, the decreasing trend is not monotonic. Further, the detailed analysis of TT events combining macroscopic Schmid factor and the geometric measures (m’: accounts for the alignment of both twin plane normal and shear directions; m”: accounts for the alignment of only twin shear directions; and m”’: accounts for the alignment of only twin plane normal) helps in understanding and identifying the process of twin-pair formation, i.e., co-nucleation versus transmission, also to identify the role of local stresses at GBs induced by inter-grain interaction versus twinning shear transformation processes. In addition, Bayesian inference is used to draw statistically meaningful conclusions as to the likelihood of transmission given misorientation angles. Lastly, twin chain frequency as a function of chain length is predicted using the probability distribution obtained from the Bayesian inference and compared with the actual data from the EBSD microstructures.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Nuclear Structure and Decay Data for A=44 Isobars

Experimental nuclear spectroscopic data are evaluated for 12 known nuclides of mass number A=44 (Si, P, S, Cl, Ar, K, Ca, Sc, Ti, V, Cr, Mn). Detailed evaluated information are presented for each reaction and decay. Recommended values combining all available data are provided for all spectroscopic properties of each level, γ-ray, and decay radiation. No excited states have yet been identified in 44 Si, 44 P, 44 Cr, and 44 Mn. Information for excited states in 44 Cl and 44 V are limited. Nuclides of 44 S, 44 Ar and 44 K have been studied via only a few reactions and decays, while 44 Ca, 44 Sc and 44 Ti are the most investigated nuclides through various reactions and decays. Evaluators note that the half-life of the g.s. of 44 S has been measured independently, with fairly good statistics, in three references, most precise being 100 ms 1 by 2004Gr20, but this value is in disagreement with the values of 125.5 ms 25 and 119 ms 6 by 2022Tr03, and 123 ms 10 by 1995So03. We adopted the unweighted average of this discrepant dataset. Another outstanding issue is that of the β + -delayed proton decay of 44 Cr g.s. to 44 V, where the T=2, 0 + IAS state in 44 V is expected to be strongly populated by a superallowed β transition, but has not been definitely identified as discussed in detail by 2020Fu05. A detailed study of 44 Cr decay is required to unravel the status of the T=2, 0 + IAS state in 44 V. Furthermore, this work supersedes earlier ENSDF evaluations of A=44 by 2011Ch39 and 1999Ca45.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Cryogenic electronics for noble liquid neutrino detectors

In this paper we present the general features of cryogenic (or “cold”) electronics for noble liquid time projection chambers, with design principles and details for neutrino physics, a brief history of the technology and details of recent research and development that is driving the design of the detectors under construction. Finally, some comments on future R&D envisioned and the impact of this work on other fields is described. “Cold” in the context of this work applies to CMOS devices operated at 77 K and above, at liquids temperatures of LAr (89 K), LKr (125 K) and LXe (165 K), with most of the tests performed in, or at LN 2 (77 K). Additionally, the paper is concentrated on the design of cold electronics for large liquid argon TPCs, those that have been successfully operated, MicroBooNE and ProtoDUNE, and those designed or under construction, such as SBND and DUNE first and second 10 kton modules. The high performance achieved with MicroBooNE and ProtoDUNE – a high signal-to-noise ratio combined with high stability of response – is mainly due to the integral approach to design and construction of sensing electrodes with cold readout electronics in a modular approach with the cryostat signal feed-throughs incorporating warm interface electronics into a Faraday cage with the cryostat. The integral concept is described in some detail in this paper.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗
DOE OSTI2025

Overview of high-density QCD studies with the CMS experiment at the LHC

We review key measurements performed by CMS in the context of its heavy ion physics program, using event samples collected in 2010-2018 with several collision systems and energies. These studies provide detailed macroscopic and microscopic probes of the quark-gluon plasma (QGP) created at the LHC energies, a medium characterized by the highest temperature and smallest baryon-chemical potential ever reached in the laboratory. Numerous observables related to high-density quantum chromodynamics (QCD) were studied, leading to some of the most impactful and qualitatively novel results in the 40-year history of the field. Using a dedicated high-multiplicity trigger in the first pp run, CMS discovered that small collision systems can exhibit signs of collectivity, a generic phenomenon with significant implications and presently understood to affect essentially all soft physics processes. This observation opened new paths to understand how fluidity and plasma properties emerge in QCD matter as a function of system size. Measurements of jet quenching have reached a completely new level of detail by directly assessing, for the first time, the medium modification of parton showers, as opposed to simply observing leading hadrons or di-hadrons. The first fully reconstructed beauty hadron and heavy-flavor jet nuclear modifications were also measured. The large size of the event samples, the precision of the measurements, and the extension of the probed kinematical phase space, allowed many other hard probes of the QGP medium to be explored in detail, leading to multiple groundbreaking findings. In particular, the seminal measurements of bottomonium suppression patterns answer fundamental questions that have been actively pursued, both theoretically and experimentally, by the community since the mid-1980s. We conclude by outlining the opportunities offered by the continuation of this physics program at the LHC.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Insight into premixed diethoxymethane flames: Laminar burning velocities, temperatures, and emissions behaviour

Diethoxymethane ((CH 3 CH 2 O) 2 CH 2 , DEM) is a promising carbon-neutral fuel. DEM is a diether or acetal with a molecular structure similar to oxymethylene ethers (CH 3 O–(CH 2 O)n–CH 3 , OME n ). Thus, DEM can be expected to have a similar combustion behavior to OMEs, reducing harmful emissions such as NO x and particulate matter (PM) in internal combustion engines. From both experimental and kinetic modeling, fundamental studies on DEM are scarce in the literature. More studies are required to gain a detailed insight into the oxidation kinetics of DEM. Laminar burning velocity (LBV) is a critical property that allows a detailed assessment of the potential application of DEM in combustion devices. Unfortunately, the literature on the LBV of DEM is limited. Therefore, in this study we have investigated the LBV of DEM using two reactors for the first time, namely a heat flux burner and a combustion chamber. The experimental data is reported for equivalence ratio between 0.7 and 1.7, initial temperatures of 368–423 K, and initial pressure of 1–5 bar. In addition, we developed a detailed kinetic model extending our recent work of Shrestha et al. (Combust. Flame. 246 (2022) 112,426) to characterize the combustion behavior of DEM utilizing the new experimental data from this work and the literature data. Our model performs remarkably well in capturing the newly measured LBV experimental data over various experimental conditions. We found that DEM and dimethoxy methane (DMM) have similar values of LBVs (within ±1.5 cm/s) for a given condition, which indicates that intermediate chemistry governs the flame chemistry. Despite DEM being a larger molecule that is expected to have slightly lower LBVs than DMM, its effect on the measured values of LBVs is negligible. Finally, we experimentally measured NO x formation in DEM flame for the first time. The stochiometric flame has the highest NO x formation. The proposed model predicted the equivalence ratio dependence of NO x nicely. However, it overestimates the NO x formation for stoichiometric DEM/air mixtures by ~30 %. The model suggests that the thermal NO formation route is favored at lean and stochiometric conditions. In contrast, the prompt NO formation route is enhanced for rich mixtures.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Analysis of soot formation from aviation fuels in laminar counterflow flames

Combustion emissions from aviation contribute to the formation of condensation trail (contrail) that can lead to the formation of anthropogenic cirrus clouds. Ice particles that form contrails are observed to have a linear correlation with soot particle number density. Synthetic aviation fuels (SAFs) offer a promising route to mitigate the production of soot particles while also increasing energy security. Although studies have focused on combustion and spray behavior, the detailed investigation of soot formation processes for different jet fuels and their impact on models for computational fluid dynamics (CFD) applications is not well understood. Moreover, experimental measurements of soot for canonical flames using Synthetic aviation fuels (SAF) for model validation remain scarce. To address this, we use employed the Lawrence Livermore National Laboratory (LLNL) detailed soot model based on the discrete sectional method. Additionally, we develop two reduced chemical mechanisms for Jet-A and Alcohol-to-Jet (C1) that are suitable for turbulent flame simulations and couple them with the Hybrid Method of Moments (HMOM). The detailed and reduced model frameworks are validated against experimental measurements of soot volume fraction (ƒ ν ) from a counterflow burner experiment previously reported in the literature. Given the good agreement between modeling results and experimental measurements for the (1) spatial distribution of ƒ ν and (2) the non-linear variation of peak ƒ ν with strain rate, we further investigate the modeled sub-processes (nucleation, condensation, surface growth, and oxidation) using the LLNL model to analyze the assumptions in the reduced model framework. Furthermore, the results indicate a significant contribution from resonant radicals to the surface growth of soot particles, which are not accounted for in the current implementation of HMOM and could help reconcile soot predictions by the reduced model with observations.

Counterflow↗
DOE OSTI2026

ab initio Sub-Mechanism Development for Cyclopentene Oxidation

To accurately predict low-temperature oxidation behavior, chemical kinetics mechanisms must contain complete reaction networks that include detailed consumption reactions of intermediates produced directly from hydroperoxyalkyl radicals, Q̇OOH, which undergo competing unimolecular reactions and bimolecular reactions with O2. Rates of chain-branching are governed by the flux between the two competing pathways, and inherently depend on temperature, pressure, and oxygen concentration. Neglect of consumption pathways for major oxidation intermediates leads to mechanism truncation error that is ameliorated by expanding the level of detail included in sub-mechanisms and employing ab initio methods for computing rates of elementary reactions and thermochemical properties of species involved. In the present work, an ab initio-derived sub-mechanism is developed using AutoMech to model the chemical kinetics of cyclopentene, a major product of cyclopentane oxidation. The ab initio sub-mechanism builds on a detailed mechanism developed using Reaction Mechanism Generator (RMG) for the specific purpose of determining the extent to which replacing cyclopentene-specific reactions and species with quantum chemical computations reduces model inaccuracies resulting from mechanism truncation error. In an effort to minimize interference from other reactions present during the formation of cyclopentene from cyclopentyl + O2, providing a narrower experimental scope, the model is compared against speciation measurements from jet-stirred reactor (JSR) experiments on cyclopentene oxidation. The experiments utilize vacuum ultraviolet-absorption spectroscopy and mass spectrometry for isomer-resolved speciation of intermediates at 835 Torr from 700 – 950 K. [O2]-dependent experiments were also conducted from 0.057 – 2.01 · 1018 molecules cm–3 at 825 K to examine the influence of oxygen on species profiles. Model predictions using the ab initio-revised mechanism yielded significant improvements in species profiles for both the temperature- and [O2]-dependent measurements, owing in part to increased rates of HOȮ and H2O2 production, which underscores the influence of theoretical calculations of reaction rates involving species produced from Ṙ + O2 such as cyclopentene.

AutoMech↗