Hydrogen ejection from hydrocarbons: Characterization and relevance in soot formation and interstellar chemistry.

Polycyclic aromatic hydrocarbons (PAHs) play a major role in the chemistry of combustion, pyrolysis, and the interstellar medium. Production (or activation) of radical PAHs and propagation of their resulting reactions require efficient dehydrogenation, but the preferred method of hydrogen loss is not well understood. Unimolecular hydrogen ejection (i.

WindCline: Sloping wind tunnel for characterizing flame behavior under variable inclines and wind conditions.

Developing accurate computational models of wildfire dynamics is increasingly important due to the substantial and expanding negative impacts of wildfire events on human health, infrastructure, and the environment. Wildfire spread and emissions depend on a number of factors, including fuel type, environmental conditions (moisture, wind speed, etc.), and terrain/location.

The Identity and Chemistry of CH Radicals Observed during Soot Formation.

We used aerosol mass spectrometry coupled with tunable synchrotron photoionization to measure radical and closed-shell species associated with particle formation in premixed flames and during pyrolysis of butane, ethylene, and methane. We analyzed photoionization (PI) spectra for the CH radical to identify the isomers present during particle formation. For the combustion and pyrolysis of all three fuels, the PI spectra can be fit reasonably well with contributions from four radical isomers: benzyl, tropyl, vinylcyclopentadienyl, and -tolyl.

Comprehensive Kinetics on the CH Potential Energy Surface under Combustion Conditions.

The automated kinetics workflow code, KinBot, was used to explore and characterize the regions of the CH potential energy surface that are relevant to combustion environments and especially soot inception. We first explored the lowest-energy region, which includes the benzyl, fulvenallene + H, and cyclopentadienyl + acetylene entry points. We then expanded the model to include two higher-energy entry points, vinylpropargyl + acetylene and vinylacetylene + propargyl.

Automated Reaction Kinetics of Gas-Phase Organic Species over Multiwell Potential Energy Surfaces.

Automation of rate-coefficient calculations for gas-phase organic species became possible in recent years and has transformed how we explore these complicated systems computationally. Kinetics workflow tools bring rigor and speed and eliminate a large fraction of manual labor and related error sources. In this paper we give an overview of this quickly evolving field and illustrate, through five detailed examples, the capabilities of our own automated tool, KinBot.

Distinguishing Gas-Phase and Nanoparticle Contributions to Small-Angle X-ray Scattering in Reacting Aerosol Flows.

We have developed a strategy for distinguishing between small-angle X-ray scattering (SAXS) from gas-phase species and newly formed nanoparticles in mixed gas- and particle-phase reacting flows. This methodology explicitly accounts for temperature-dependent scattering from gases. We measured SAXS in a sooting linear laminar partially premixed co-flow ethylene/air diffusion flame.

A Review of Terminology Used to Describe Soot Formation and Evolution under Combustion and Pyrolytic Conditions.

This review presents a glossary and review of terminology used to describe the chemical and physical processes involved in soot formation and evolution and is intended to aid in communication within the field and across disciplines. There are large gaps in our understanding of soot formation and evolution and inconsistencies in the language used to describe the associated mechanisms. These inconsistencies lead to confusion within the field and hinder progress in addressing the gaps in our understanding.

Photoionization Efficiencies of Five Polycyclic Aromatic Hydrocarbons.

We have measured photoionization-efficiency curves for pyrene, fluoranthene, chrysene, perylene, and coronene in the photon energy range of 7.5-10.2 eV and derived their photoionization cross-section curves in this energy range.

Critical Assessment of Photoionization Efficiency Measurements for Characterization of Soot-Precursor Species.

We present a critical evaluation of photoionization efficiency (PIE) measurements coupled with aerosol mass spectrometry for the identification of condensed soot-precursor species extracted from a premixed atmospheric-pressure ethylene/oxygen/nitrogen flame. Definitive identification of isomers by any means is complicated by the large number of potential isomers at masses likely to comprise particles at flame temperatures. This problem is compounded using PIE measurements by the similarity in ionization energies and PIE-curve shapes among many of these isomers.

Flame experiments at the advanced light source: new insights into soot formation processes.

The following experimental protocols and the accompanying video are concerned with the flame experiments that are performed at the Chemical Dynamics Beamline of the Advanced Light Source (ALS) of the Lawrence Berkeley National Laboratory(1-4). This video demonstrates how the complex chemical structures of laboratory-based model flames are analyzed using flame-sampling mass spectrometry with tunable synchrotron-generated vacuum-ultraviolet (VUV) radiation. This experimental approach combines isomer-resolving capabilities with high sensitivity and a large dynamic range(5,6).

Toward verifying fossil fuel CO2 emissions with the CMAQ model: motivation, model description and initial simulation.

Unlabelled: Motivated by the question of whether and how a state-of-the-art regional chemical transport model (CTM) can facilitate characterization of CO2 spatiotemporal variability and verify CO2 fossil-fuel emissions, we for the first time applied the Community Multiscale Air Quality (CMAQ) model to simulate CO2. This paper presents methods, input data, and initial results for CO2 simulation using CMAQ over the contiguous United States in October 2007. Modeling experiments have been performed to understand the roles of fossil-fuel emissions, biosphere-atmosphere exchange, and meteorology in regulating the spatial distribution of CO2 near the surface over the contiguous United States.

Complications to optical measurements using a laser with an unstable resonator: a case study on laser-induced incandescence of soot.

Temporal behavior of pulses from a Q-switched Nd:YAG laser with an unstable resonator can vary significantly with radial position in the beam. Our laser provides pulses with position-dependent durations spanning 8-11.5 ns at 1064 nm and 7-10 ns at 532 nm.

Spontaneous emission from the C3 radical in carbon plasma.

Spontaneous emission measurements are discussed for the Swings transitions of the C(3) radical in laser-generated graphite plasma, and the spectroscopy of the C(3) radical in carbon vapor and plasma is summarized. A review is given of some theoretical calculations and emission spectroscopic investigations are presented. Time-averaged, laser-induced optical breakdown spectra are reported from Nd:YAG laser generated graphite microplasma.

Particle formation from pulsed laser irradiation of soot aggregates studied with a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope.

We investigated the physical and chemical changes induced in soot aggregates exposed to laser radiation using a scanning mobility particle sizer, a transmission electron microscope, and a scanning transmission x-ray microscope to perform near-edge x-ray absorption fine structure spectroscopy. Laser-induced nanoparticle production was observed at fluences above 0.12 J/cm(2) at 532 nm and 0.

Time-resolved laser-induced incandescence of soot: the influence of experimental factors and microphysical mechanisms.

We present a data set for testing models of time-resolved laser-induced incandescence of soot. Measurements were made in a laminar ethene diffusion flame over a wide range of laser fluences at 532 nm. The laser was seeded to provide a smooth temporal profile, and the beam was spatially filtered and imaged into the flame to provide a homogeneous spatial profile.

Atmospheric Trace Molecule Spectroscopy (ATMOS) Experiment Version 3 data retrievals.

Version 3 of the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment data set for some 30 trace and minor gas profiles is available. From the IR solar-absorption spectra measured during four Space Shuttle missions (in 1985, 1992, 1993, and 1994), profiles from more than 350 occultations were retrieved from the upper troposphere to the lower mesosphere. Previous results were unreliable for tropospheric retrievals, but with a new global-fitting algorithm profiles are reliably returned down to altitudes as low as 6.