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Miller, James A.

Publications and source records attributed to Miller, James A..

At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Quantifying the Relevance of Prompt Dissociations of Resonance Stabilized Free Radicals in Flames

In prior studies from our laboratory we have shown that weakly-bound free radicals have a propensity to promptly dissociate at elevated temperatures relevant to flames. Dissociation can occur so rapidly at high temperatures in such weakly-bound radicals that it interferes with collisional relaxation of internal energies leading to prompt dissociation. While prompt dissociation is a ubiquitous feature in such free radical dissociations, we have hypothesized that its relevance to global combustion observables such as flame speeds depends on satisfying specific criteria. Two criteria that motivate the present study are that the free radicals must play a central role in the oxidation mechanism and that their thermal dissociation rate coefficients should be small enough. Resonance stabilized radicals have bond strengths ~ 50 kcal/mol (or larger) and consequently are known to dissociate slowly and persist even in high temperature environments. In this work we have calculated prompt dissociation probabilities for some simple allylic (allyl, methyl allyl, and dimethyl allyl) radicals. Flame simulations were performed to quantify the relevance of including prompt dissociations of these allylic radicals.

Allyl Radicals↗
DOE OSTI2021

Combustion chemistry in the twenty-first century: Developing theory-informed chemical kinetics models

Over the past 20 to 25 years theoretical chemistry (particularly theoretical chemical kinetics) has played an increasingly important role in developing chemical kinetics models for combustion. Theoretical methods of obtaining rate parameters are now competitive in accuracy with experiment, particularly for small molecules. Moreover, theoretical methods can deal with conditions that experiments frequently cannot. In addition to increased accuracy, theory has rejuvenated methods and discovered phenomena that were completely unappreciated, or at least underappreciated, in the 20th century. Our primary interest here is in molecular-level issues, i.e. in calculating rate and transport parameters. However, dealing with kinetics models that involve thousands of reactions and hundreds of species is important for practical applications and is relatively new to the 21st century. Theory, in a general sense, and theoretical methods development have a role to play here too. We discuss in this review all these topics in some detail with an emphasis on issues and methods that have emerged in the last 20 years or so. Even so, our review is selective, rather than comprehensive, out of necessity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Reference Natural Gas Flames at Nominally Autoignitive Engine-Relevant Conditions

Laminar natural gas flames are investigated at engine-relevant thermochemical conditions where the ignition delay time r is short due to very high ambient temperatures and pressures. At these conditions, it is not possible to measure or calculate well-defined values for the laminar flame speed S-l, laminar flame thickness delta(l), and laminar flame time scale tau(l) = delta(l)/S-l due to the explosive thermochemical state. Here, the corresponding reference values, S-R, delta(R), and tau(R) = S-R/S-R, that account for the effects of autoignition, are numerically estimated to investigate the enhancement of flame propagation, and the competition with autoignition that arises under nominally autoignitive conditions (characterised here by the number tau/tau(R)). Large values of tau/tau(R) indicate that autoignition is unimportant, values near or below unity indicate that flame propagation is not possible, and intermediate values indicate that a combination of both flame propagation and autoignition may be important, depending upon factors such as device geometry, turbulence, stratification, et cetera. The reference quantities are presented for a wide range of temperatures, equivalence ratios, pressures, and hydrogen concentrations, which includes conditions relevant to stationary gas turbine reheat burners and boosted spark ignition engines. It is demonstrated that the transition from flame propagation to autoignition is only dependent on residence time, when the results are non-dimensionalised by the reference values. The temporal evolution of the reference values are also reported for a modelled boosted SI engine. It is shown that the nominally autoignitive conditions enhance flame propagation, which may be an ameliorating factor for the onset of engine knock. The calculations are performed using a recently-developed, detailed 177 species mechanism for C0-C3 chemistry that is derived from theoretical chemistry and is suitable for a wide range of thermochemical conditions as it is not tuned or optimised for a particular operating condition. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.

autoignition↗
DOE OSTI2018

Modeling nitrogen chemistry in combustion

Understanding of the chemical processes that govern formation and destruction of nitrogen oxides (NO x ) in combustion processes continues to be a challenge. Even though this area has been the subject of extensive research over the last four decades, there are still unresolved issues that may limit the accuracy of engineering calculations and thereby the potential of primary measures for NO x control. In this review our current understanding of the mechanisms that are responsible for combustion-generated nitrogen-containing air pollutants is discussed. The thermochemistry of the relevant nitrogen compounds is updated, using the Active Thermochemical Tables (ATcT) approach. Rate parameters for the key gas-phase reactions of the nitrogen species are surveyed, based on available information from experiments and high-level theory. The mechanisms for thermal and prompt-NO, for fuel-NO, and NO formation via NNH or N 2 O are discussed, along with the chemistry of NO removal processes such as reburning and Selective Non-Catalytic Reduction of NO. Each subset of the mechanism is evaluated against experimental data and the accuracy of modeling predictions is discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Initiation reactions in acetylene pyrolysis

In gas-phase combustion systems the interest in acetylene stems largely from its role in molecular weight growth processes. The consensus is that above 1500 K acetylene pyrolysis starts mainly with the homolytic fission of the C–H bond creating an ethynyl radical and an H atom. However, below ~1500 K this reaction is too slow to initiate the chain reaction. It has been hypothesized that instead of dissociation, self-reaction initiates this process. Nevertheless, rigorous theoretical or direct experimental evidence is lacking, to an extent that even the molecular mechanism is debated in the literature. In this work we use rigorous ab initio transition-state theory master equation methods to calculate pressure- and temperature-dependent rate coefficients for the association of two acetylene molecules and related reactions. We establish the role of vinylidene, the high-energy isomer of acetylene in this process, compare our results with available experimental data, and assess the competition between the first-order and second-order initiation steps. As a result, we also show the effect of the rapid isomerization among the participating wells and highlight the need for time-scale analysis when phenomenological rate coefficients are compared to observed time scales in certain experiments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Theoretical kinetics of O + C 2 H 4

The reaction of atomic oxygen with ethylene is a fundamental oxidation step in combustion and is prototypical of reactions in which oxygen adds to double bonds. For 3 O+C 2 H 4 and for this class of reactions generally, decomposition of the initial adduct via spin-allowed reaction channels on the triplet surface competes with intersystem crossing (ISC) and a set of spin-forbidden reaction channels on the ground-state singlet surface. The two surfaces share some bimolecular products but feature different intermediates, pathways, and transition states. In addition, the overall product branching is therefore a sensitive function of the ISC rate. The 3 O+C 2 H 4 reaction has been extensively studied, but previous experimental work has not provided detailed branching information at elevated temperatures, while previous theoretical studies have employed empirical treatments of ISC. Here we predict the kinetics of 3 O+C 2 H 4 using an ab initio transition state theory based master equation (AITSTME) approach that includes an a priori description of ISC. Specifically, the ISC rate is calculated using Landau–Zener statistical theory, consideration of the four lowest-energy electronic states, and a direct classical trajectory study of the product branching immediately after ISC. The present theoretical results are largely in good agreement with existing low-temperature experimental kinetics and molecular beam studies. Good agreement is also found with past theoretical work, with the notable exception of the predicted product branching at elevated temperatures. Above ~1000 K, we predict CH 2 CHO+H and CH 2 +CH 2 O as the major products, which differs from the room temperature preference for CH 3 +HCO (which is assumed to remain at higher temperatures in some models) and from the prediction of a previous detailed master equation study.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Weakly Bound Free Radicals in Combustion: "Prompt" Dissociation of Formyl Radicals and Its Effect on Laminar Flame Speeds

Weakly bound free radicals have low-dissociation thresholds such that at high temperatures, timescales for dissociation and collisional relaxation become comparable, leading to significant dissociation during the vibrational-rotational relaxation process. Here we characterize this “prompt” dissociation of formyl (HCO), an important combustion radical, using direct dynamics calculations for OH + CH2O and H + CH2O (key HCO-forming reactions). For all other HCO-forming reactions, presumption of a thermal incipient HCO distribution was used to derive prompt dissociation fractions. Inclusion of these theoretically derived HCO prompt dissociation fractions into combustion kinetics models provides an additional source for H-atoms that feeds chain branching reactions. Simulations using these updated combustion models are therefore shown to enhance flame propagation in 1,3,5-trioxane and acetylene. The present results suggest that HCO prompt dissociation should be included when simulating flames of hydrocarbons and oxygenated molecules and that prompt dissociations of other weakly bound radicals may also impact combustion simulations

Dynamics↗
DOE OSTI2014

First-principles binary diffusion coefficients for H, H 2 and four normal alkanes + N 2

Collision integrals related to binary (dilute gas) diffusion are calculated classically for six species colliding with N 2 . The most detailed calculations make no assumptions regarding the complexity of the potential energy surface, and the resulting classical collision integrals are in excellent agreement with previous semiclassical results for H + N 2 and H 2 + N 2 and with recent experimental results for C n H 2n+2 + N 2 , n = 2–4. The detailed classical results are used to test the accuracy of three simplifying assumptions typically made when calculating collision integrals: (1) approximating the intermolecular potential as isotropic, (2) neglecting the internal structure of the colliders (i.e., neglecting inelasticity), and (3) employing unphysical R –12 repulsive interactions. The effect of anisotropy is found to be negligible for H + N 2 and H 2 + N 2 (in agreement with previous quantum mechanical and semiclassical results for systems involving atomic and diatomic species) but is more significant for larger species at low temperatures. For example, the neglect of anisotropy decreases the diffusion coefficient for butane + N 2 by 15% at 300 K. The neglect of inelasticity, in contrast, introduces only very small errors. Approximating the repulsive wall as an unphysical R –12 interaction is a significant source of error at all temperatures for the weakly interacting systems H + N 2 and H 2 + N 2 , with errors as large as 40%. For the normal alkanes in N 2 , which feature stronger interactions, the 12/6 Lennard–Jones approximation is found to be accurate, particularly at temperatures above –700 K where it predicts the full-dimensional result to within 5% (although with somewhat different temperature dependence). Overall, the typical practical approach of assuming isotropic 12/6 Lennard–Jones interactions is confirmed to be suitable for combustion applications except for weakly interacting systems, such as H + N 2 . For these systems, anisotropy and inelasticity can safely be neglected but a more detailed description of the repulsive wall is required for quantitative predictions. Moreover, a straightforward approach for calculating effective isotropic potentials with realistic repulsive walls is described. An analytic expression for the calculated diffusion coefficient for H + N 2 is presented and is estimated to have a 2-sigma error bar of only 0.7%.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2014

Adventures on the C 3 H 5 O potential energy surface: OH+propyne, OH+allene and related reactions

We mapped out the stationary points and the corresponding conformational space on the C 3 H 5 O potential energy surface relevant for the OH + allene and OH + propyne reactions systematically and automatically using the KinBot software at the UCCSD(T)-F12b/cc-pVQZ-F12//M06-2X/6-311++G(d,p) level of theory. We used RRKM-based 1-D master equations to calculate pressure- and temperature-dependent, channel-specific phenomenological rate coefficients for the bimolecular reactions propyne + OH and allene + OH, and for the unimolecular decomposition of the CH 3 CCHOH, CH 3 C(OH)CH, CH 2 CCH 2 OH, CH 2 C(OH)CH 2 primary adducts, and also for the related acetonyl, propionyl, 2-methylvinoxy, and 3-oxo-1-propyl radicals. The major channel of the bimolecular reactions at high temperatures is the formation propargyl + H 2 O, which makes the title reactions important players in soot formation at high temperatures. However, below ~1000 K the chemistry is more complex, involving the competition of stabilization, isomerization and dissociation processes. We found that the OH addition to the central carbon of allene has a particularly interesting and complex pressure dependence, caused by the low-lying exit channel to form ketene + CH 3 bimolecular products. In this study, we compared our results to a wide range of experimental data and assessed possible uncertainties arising from certain aspects of the theoretical framework.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2003

Production of Loop-Top Hard X-Ray Emission

The main goal of this work has been to understand the particle acceleration mechanism (or mechanisms) in impulsive solar flares, using hard X-ray observations of high spatial and spectral resolution. Several new observations, including the observations by YOHKOH that reveal emission from both footpoints and loop tops, have suggested to us that a model employing stochastic acceleration is the most likely candidate for explaining energetic particles in a majority (if not all) of impulsive flares. In this model, most of the flare energy is initially converted into plasma waves and turbulence, which in turn can accelerate particles from thermal to relativistic energies on sub-second timescales. This research has provided important tools for the interpretation of the high spectral and spatial resolution observations obtained from the Ramaty High Energy Solar Spectroscopic Imager (RHESSI) . In the course of our research, we have focused on two different (but possibly related) stochastic acceleration models: (1) a model that employs high-frequency whistler turbulence and concentrates on the energetic electrons, and (2) a model that employs low frequency MHD waves, and is able to accelerate both the ambient electrons and ions.

Miller, James A.↗
NASA NTRS2001

Stochastic Particle Acceleration in Impulsive Solar Flares

The acceleration of a huge number of electrons and ions to relativistic energies over timescales ranging from several seconds to several tens of seconds is the fundamental problem in high-energy solar physics. The cascading turbulence model we have developed has been shown previously (e.g., Miller 2000; Miller & Roberts 1995; Miner, LaRosa, & Moore 1996) to account for all the bulk features (such as acceleration timescales, fluxes, total number of energetic particles, and maximum energies) of electron and proton acceleration in impulsive solar flares. While the simulation of this acceleration process is involved, the essential idea of the model is quite simple, and consists of just a few parts: 1. During the primary flare energy release phase, we assume that low-amplitude MHD Alfven and fast mode waves are excited at long wavelengths, say comparable to the size of the event (although the results are actually insensitive to this initial wavelength). While an assumption, this appears reasonable in light of the likely highly turbulent nature of the flare. 2. These waves then cascade in a Kolmogorov-like fashion to smaller wavelengths (e.g., Verma et al. 1996), forming a power-law spectral density in wavenumber space through the inertial range. 3. When the mean wavenumber of the fast mode waves has increased sufficiently, the transit-time acceleration rate (Miller 1997) for superAlfvenic electrons can overcome Coulomb energy losses, and these electrons are accelerated out of the thermal distribution and to relativistic energies (Miller et al. 1996). As the Alfven waves cascade to higher wavenumbers, they can cyclotron resonate with progressively lower energy protons. Eventually, they will resonate with protons in the tail of the thermal distribution, which will then be accelerated to relativistic energies as well (Miller & Roberts 1995). Hence, both ions and electrons are stochastically accelerated, albeit by different mechanisms and different waves. 4. When the protons become superAlfvenic (above about 1 MeV/nucleon), they too can suffer transit-time acceleration by the fast mode waves and will receive an extra acceleration "kick." The basic overall objective of this 1 year effort was to construct a spatially-dependent version of this acceleration model and this has been realized.

Miller, James A.↗
NASA NTRS1999

Anticipating HESSI's View of Spectral Evolution in Flare Hard X-Ray Emission

The spectral evolution of observed flares' hard X-ray emission is found to conform to certain patterns in color-color diagrams (CCDs). By combining the spectral resolution of BATSE data with the spatial resolution of HXT data, we are able to address the nature of flare energy release and anticipate what kind of observations HESSI may make of the energy release/particle acceleration site in flares. The implications of these observations for theoretical models of acceleration and propagation is considered.

Newton, Elizabeth K.↗