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NASA NTRS1992

Benefits and limitations of composites in carrier-based aircraft

There are many unique aspects of Navy air missions that lead to the differentiation between the design and performance of ship and shore-based aircraft. The major aspects are discussed from which essentially all Navy aircraft design requirements derive. (1) Navy aircraft operate from carriers at sea imposes a broad spectrum of physical conditions, constraints, and requirements ranging from the harsh sea environment, the space limitations of a carrier, takeoff and landing requirements as well as for endurance at long distances from the carrier. (2) Because the carrier and its airwing are intended to be capable of responding to a broad range of contingencies, mission flexibility is essential (maximum weapon carriage, rapid reconfiguration, multiple mission capability). (3) The embarked aircraft provides the long range defense of the battle group against air, surface and subsurface launched antiship missiles. (4) The carrier and its aircraft must operate independently and outside of normal supply lines. Taking into account these aspects, the use of composite materials in the design and performance of naval aircraft is outlined, also listing advantages and disadvantages.

Mcerlean, Donald P.↗

NASA NTRS2001

Estimating Expressed Temperature and Fractional Area of Hot Lava at the Kilauea Vent with AVIRIS Spectral Measurements

Imaging spectroscopy offers a framework based in physics and chemistry for scientific investigation of a wide range of phenomena of interest in the Earth environment. In the scientific discipline of volcanology knowledge of lava temperature and distribution at the surface provides insight into the volcano status and subsurface processes. A remote sensing strategy to measure surface lava temperatures and distribution would support volcanology research. Hot targets such as molten lava emit spectral radiance as a function of temperature. A figure shows a series of Planck functions calculated radiance spectra for hot targets at different temperatures. A maximum Lambertian solar reflected radiance spectrum is shown as well. While similar in form, each hot target spectrum has a unique spectral shape and is distinct from the solar reflected radiance spectrum. Based on this temperature-dependent signature, imaging spectroscopy provides an innovative approach for the remote-sensing-based measurement of lava temperature. A natural site for investigation of the measurement of lava temperature is the Big Island of Hawaii where molten lava from the Kilauea vent is present at the surface. In the past, Airborne Visible/Infrared Imaging Spectrometer (AVIRIS) data sets have been used for the analysis of hot volcanic targets and hot burning fires. The research presented here builds upon and extends this earlier work. The year 2000 Hawaii AVIRIS data set has been analyzed to derive lava temperatures taking into account factors of fractional fill, solar reflected radiance, and atmospheric attenuation of the surface emitted radiance. The measurements, analyses, and current results for this research are presented here.

Green, Robert O.↗

DOE OSTI2023

Modulating Electronic Structure of Atomically Dispersed Nickel Sites through Boron and Nitrogen Dual Coordination Boosts Oxygen Reduction

Abstract Atomically dispersed 3D transitional metal active sites with nitrogen coordination anchored on carbon support have emerged as a kind of promising electrocatalyst toward oxygen reduction reaction (ORR) in the field of fuel cells and metal–air cells. However, it is still a challenge to accurately modulate the coordination structure of single‐atom metal sites, especially first‐shell coordination, as well as identify the relationship between the geometric/electronic structure and ORR performance. Herein, a carbon‐supported single‐atom nickel catalyst is fabricated with boron and nitrogen dual coordination (denoted as Ni‐B/N‐C). The hard X‐ray absorption spectrum result reveals that atomically dispersed Ni active sites are coordinated with one B atom and three N atoms in the first shell (denoted as Ni‐B 1 N 3 ). The Ni‐B/N‐C catalyst exhibits a half‐wave potential ( E 1/2 ) of 0.87 V versus RHE, along with a distinguished long‐term durability in alkaline media, which is superior to commercial Pt/C. Density functional theory calculations indicate that the Ni‐B 1 N 3 active sites are more favorable for the adsorption of ORR intermediates relative to Ni‐N 4 , leading to the reduction of thermodynamic barrier and the acceleration of reaction kinetics, which accounts for the increased intrinsic activity.

Chemistry↗

DOE OSTI2021

Clustering of CODEX clusters

The clustering of galaxy clusters links the spatial nonuniformity of dark matter halos to the growth of the primordial spectrum of perturbations. The amplitude of the clustering signal is widely used to estimate the halo mass of astrophysical objects. The advent of cluster mass calibrations enables using clustering in cosmological studies. Aims. We analyze the autocorrelation function of a large contiguous sample of galaxy clusters, the Constrain Dark Energy with X-ray (CODEX) sample, in which we take particular care of cluster definition. These clusters were X-ray selected using the ROentgen SATellite All-Sky Survey and then identified as galaxy clusters using the code redMaPPer run on the photometry of the Sloan Digital Sky Survey. We develop methods for precisely accounting for the sample selection effects on the clustering and demonstrate their robustness using numerical simulations. Methods. Using the clean CODEX sample, which was obtained by applying a redshift-dependent richness selection, we computed the two-point autocorrelation function of galaxy clusters in the 0.1 < z < 0.3 and 0.3 < z < 0.5 redshift bins. We compared the bias in the measured correlation function with values obtained in numerical simulations using a similar cluster mass range. Results. By fitting a power law, we measured a correlation length r 0 = 18.7 ± 1.1 and slope γ = 1.98 ± 0.14 for the correlation function in the full redshift range. By fixing the other cosmological parameters to their nine-year Wilkinson Microwave Anisotropy Probe values, we reproduced the observed shape of the correlation function under the following cosmological conditions: Ω m0 = $0.22_{-0.03}^{+0.04}$ and S 8 = σ 8 (Ω m0 /0.3)0.5 = $0.85_{-0.08}^{+0.10}$ with estimated additional systematic errors of σ Ω m0 = 0.02 and σS 8 = 0.20. We illustrate the complementarity of clustering constraints by combining them with CODEX cosmological constraints based on the X-ray luminosity function, deriving Ωm = 0.25 ± 0.01 and σ 8 = $0.81_{-0.02}^{+0.01}$ with an estimated additional systematic error of σ Ω m0 = 0.07 and σ σ8 = 0.04. The mass calibration and statistical quality of the mass tracers are the dominant source of uncertainty.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2013

X-RAY POINT-SOURCE POPULATIONS CONSTITUTING THE GALACTIC RIDGE X-RAY EMISSION

Apparently diffuse X-ray emission has been known to exist along the central quarter of the Galactic Plane since the beginning of X-ray astronomy; this is referred to as the Galactic Ridge X-ray emission (GRXE). Recent deep X-ray observations have shown that numerous X-ray point sources account for a large fraction of the GRXE in the hard band (2-8 keV). However, the nature of these sources is poorly understood. Using the deepest X-ray observations made in the Chandra bulge field, we present the result of a coherent photometric and spectroscopic analysis of individual X-ray point sources for the purpose of constraining their nature and deriving their fractional contributions to the hard-band continuum and Fe K line emission of the GRXE. Based on the X-ray color-color diagram, we divided the point sources into three groups: A (hard), B (soft and broad spectrum), and C (soft and peaked spectrum). The group A sources are further decomposed spectrally into thermal and non-thermal sources with different fractions in different flux ranges. From their X-ray properties, we speculate that the group A non-thermal sources are mostly active galactic nuclei and the thermal sources are mostly white dwarf (WD) binaries such as magnetic and non-magnetic cataclysmic variables (CVs), pre-CVs, and symbiotic stars, whereas the group B and C sources are X-ray active stars in flares and quiescence, respectively. In the log N-log S curve of the 2-8 keV band, the group A non-thermal sources are dominant above Almost-Equal-To 10{sup -14} erg cm{sup -2} s{sup -1}, which is gradually taken over by Galactic sources in the fainter flux ranges. The Fe K{alpha} emission is mostly from the group A thermal (WD binaries) and the group B (X-ray active stars) sources.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2014

Toward the standard population synthesis model of the X-ray background: Evolution of X-ray luminosity and absorption functions of active galactic nuclei including Compton-thick populations

We present the most up to date X-ray luminosity function (XLF) and absorption function of active galactic nuclei (AGNs) over the redshift range from 0 to 5, utilizing the largest, highly complete sample ever available obtained from surveys performed with Swift/BAT, MAXI, ASCA, XMM-Newton, Chandra, and ROSAT. The combined sample, including that of the Subaru/XMM-Newton Deep Survey, consists of 4039 detections in the soft (0.5-2 keV) and/or hard (>2 keV) band. We utilize a maximum likelihood method to reproduce the count rate versus redshift distribution for each survey, by taking into account the evolution of the absorbed fraction, the contribution from Compton-thick (CTK) AGNs, and broadband spectra of AGNs, including reflection components from tori based on the luminosity- and redshift-dependent unified scheme. We find that the shape of the XLF at z ∼ 1-3 is significantly different from that in the local universe, for which the luminosity-dependent density evolution model gives much better description than the luminosity and density evolution model. These results establish the standard population synthesis model of the X-ray background (XRB), which well reproduces the source counts, the observed fractions of CTK AGNs, and the spectrum of the hard XRB. The number ratio of CTK AGNs to the absorbed Compton-thin (CTN) AGNs is constrained to be ≈0.5-1.6 to produce the 20-50 keV XRB intensity within present uncertainties, by assuming that they follow the same evolution as CTN AGNs. The growth history of supermassive black holes is discussed based on the new AGN bolometric luminosity function.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2026

Characterizing Uncertainty in Synthetic Tropical Cyclone Hazard Models for U.S. Energy Infrastructure Resilience

Tropical Cyclones (TCs) are intense storms that pose a persistent and considerable risk to coastal communities and infrastructure in the global tropics and subtropics, including the United States (US). With known limitations associated with observations and high-resolution earth system models, synthetic TC models that capture a wide spectrum of storm possibilities have been developed to robustly quantify TC risk. Here we examine the simulation of various TC features in the North Atlantic relevant for US coastal risk in three synthetic TC models forced with ERA5 reanalysis: MIT, CHAZ and RAFT. While there is a broad agreement among these models in terms of their representation of salient TC characteristics, certain differences do exist. To connect these modeling uncertainties with energy infrastructure resilience, we apply fragility curves that link simulated TC intensities to damage probabilities, demonstrating how uncertainty in storm states may translate into that in coastal impacts. Our study indicates that acknowledging and accounting for inter-model uncertainty leads to more reliable risk assessments, strengthening science-to-action pathways for managing risks associated with TCs.

Baby John, Effy↗

DOE OSTI2013

Analysis of signals under compositional noise with applications to SONAR data

In this paper, we consider the problem of denoising and classification of SONAR signals observed under compositional noise, i.e., they have been warped randomly along the x-axis. The traditional techniques do not account for such noise and, consequently, cannot provide a robust classification of signals. We apply a recent framework that: 1) uses a distance-based objective function for data alignment and noise reduction; and 2) leads to warping-invariant distances between signals for robust clustering and classification. We use this framework to introduce two distances that can be used for signal classification: a) a y-distance, which is the distance between the aligned signals; and b) an x-distance that measures the amount of warping needed to align the signals. We focus on the task of clustering and classifying objects, using acoustic spectrum (acoustic color), which is complicated by the uncertainties in aspect angles at data collections. Small changes in the aspect angles corrupt signals in a way that amounts to compositional noise. As a result, we demonstrate the use of the developed metrics in classification of acoustic color data and highlight improvements in signal classification over current methods.

47 OTHER INSTRUMENTATION↗

NASA NTRS1978

The X-ray emitting galaxy Centaurus A

OSO-8 X-ray observations of Cen A in 1975 and 1976 are reported. The source spectrum can be well fitted in both years by a power law of number index 1.66 and absorption due to 1.3 by 10 to the 23rd power atoms/sq cm. The total flux varied by a factor of 2 between 1975 and 1976. In 1976 there were flux variations of approximately 40% on a time scale of days. Measurements of the 6.4-keV Fe fluorescent line and the 7.1-keV absorption edge imply Fe/H of approximately 0.000016. Simultaneous radio measurements show variation in phase with X-ray variability. Consideration of radio, millimeter, infrared, and X-ray data shows that all the data can be accounted for by a model in which the X-rays are due to a synchrotron self-Compton source embedded in a cold H2 cloud.

Mushotzky, R. F.↗

NASA NTRS1994

Vapor Deposits in the Lunar Regolith

Since the Apollo missions, we have emphasized the following points, which are based on theoretical calculations and on laboratory studies of the properties of evaporated silicate deposits and of lunar samples. The mass of vapor generated by impacts on the lunar surface is comparable in magnitude to the mass of impact melt glasses; the physics of impact into a porous regolith requires that much of this vapor be retained in the soil rather than lost to space (as is widely believed); experimental coatings made from vaporized or sputtered lunar basalt contain abundant inclusions of submicroscopic, super paramagnetic metallic Fe; and this Fe may explain the magnetic signature, low albedo, reddened spectrum, and subdued absorption bands of lunar regolith. Our conclusions have been generally rejected by the lunar geochemical community for two reasons: there seemed to be no direct evidence for vapor deposits in Apollo samples, and it seemed that the lunar optical properties could be explained by the presence of impact melt glasses alone. However, advances in our understanding of the optical properties of glasses and of light scattering by planetary regoliths, and now the direct detection of vapor deposits, show that these objections are not valid. Vapor phase transport is a major process on the lunar surface, and unless its effects are taken into account, the chemical, magnetic, and optical properties of the regolith cannot be understood.

Hapke, Bruce↗

NASA NTRS2005

Automated Conflict Resolution For Air Traffic Control

The ability to detect and resolve conflicts automatically is considered to be an essential requirement for the next generation air traffic control system. While systems for automated conflict detection have been used operationally by controllers for more than 20 years, automated resolution systems have so far not reached the level of maturity required for operational deployment. Analytical models and algorithms for automated resolution have been traffic conditions to demonstrate that they can handle the complete spectrum of conflict situations encountered in actual operations. The resolution algorithm described in this paper was formulated to meet the performance requirements of the Automated Airspace Concept (AAC). The AAC, which was described in a recent paper [1], is a candidate for the next generation air traffic control system. The AAC's performance objectives are to increase safety and airspace capacity and to accommodate user preferences in flight operations to the greatest extent possible. In the AAC, resolution trajectories are generated by an automation system on the ground and sent to the aircraft autonomously via data link .The algorithm generating the trajectories must take into account the performance characteristics of the aircraft, the route structure of the airway system, and be capable of resolving all types of conflicts for properly equipped aircraft without requiring supervision and approval by a controller. Furthermore, the resolution trajectories should be compatible with the clearances, vectors and flight plan amendments that controllers customarily issue to pilots in resolving conflicts. The algorithm described herein, although formulated specifically to meet the needs of the AAC, provides a generic engine for resolving conflicts. Thus, it can be incorporated into any operational concept that requires a method for automated resolution, including concepts for autonomous air to air resolution.

Erzberger, Heinz↗

DOE OSTI2015

Testing secondary models for the origin of radio mini-halos in galaxy clusters

We present an MHD simulation of the emergence of a radio minihalo in a galaxy cluster core in a “secondary” model, where the source of the synchrotron-emitting electrons is hadronic interactions between cosmic-ray protons with the thermal intracluster gas, an alternative to the “reacceleration model” where the cosmic ray electrons are reaccelerated by turbulence induced by core sloshing, which we discussed in an earlier work. We follow the evolution of cosmic-ray electron spectra and their radio emission using passive tracer particles, taking into account the time-dependent injection of electrons from hadronic interactions and their energy losses. We find that secondary electrons in a sloshing cluster core can generate diffuse synchrotron emission with luminosity and extent similar to observed radio minihalos. However, we also find important differences with our previous work. We find that the drop in radio emission at cold fronts is less prominent than that in our reacceleration-based simulations, indicating that in this flavor of the secondary model the emission is more spatially extended than in some observed minihalos. We also explore the effect of rapid changes in the magnetic field on the radio spectrum. While the resulting spectra in some regions are steeper than expected from stationary conditions, the change is marginal, with differences in the synchrotron spectral index of Δα ≲ 0.15–0.25, depending on the frequency band. This is a much narrower range than claimed in the best-observed minihalos and produced in the reacceleration model. Our results provide important suggestions to constrain these models with future observations.

79 ASTRONOMY AND ASTROPHYSICS↗

DOE OSTI2023

Electronic density of states of a U ( 1 ) quantum spin liquid with spinon Fermi surface. I. Orbital magnetic field effects

A quantum spin liquid with a spinon Fermi surface is an exotic insulator that hosts neutral Fermi surfaces inside the insulating gap. In an external magnetic field, it has been pointed out that the neutral Fermi surfaces are Landau quantized to form Landau levels due to the coupling to the induced emergent gauge magnetic field. In this paper, we calculate the electronic density of states (as observed in tunneling experiments) of the quantum spin liquid in an orbital magnetic field. Here, we find that the Landau levels from the neutral Fermi surfaces give rise to a set of steps emerging at the upper and lower Hubbard band edges. Each of the Hubbard band edge steps further develop into a band edge resonance peak when a weak gauge binding arising from the gauge field fluctuations is taken into account. Importantly, each Hubbard band edge step and its resulting resonance peak in the weak gauge binding are found to have a corresponding Landau level from the neutral Fermi surfaces, so the Hubbard band edge steps and the band edge resonance peaks provide signatures to the unique feature that characterizes the Landau quantization of the in-gap neutral Fermi surfaces in the spin liquid. We further consider the strong gauge-binding regime where the band edge resonance peaks move into the Mott gap and develop into true in-gap bound states. In the strong gauge binding regime, we solve the Landau-level spectrum of the in-gap bound states in an orbital magnetic field. For the in-gap bound state with a Mexican-hat-like band dispersion, we find that the envelop energy to have a state excited from the bound state Landau levels decreases quadratically with the magnetic field. The quadratic decrease behavior of the envelop energy is consistent with the intuition that applying magnetic field localizes the states and energetically promotes the in-gap bound states formation. Finally, we discuss the connection of our results to the electronic density of states spectra measured in the layered 1T-TaS 2 . We point out that a quantum spin liquid with a quasibound state in the upper Hubbard band can give the density of states spectra similar to the one measured in the experiment.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

NASA NTRS2005

The X-Ray Weakness of GPS Radio Galaxies: A Volume-Limited Complete Sample

The XMM-Newton observations of the GPS sample was completed last summer. We are in process of finalizing the paper describing the data and the results. The main goal of the project was to determine the X-ray spectra of the GPS galaxies in comparison to regular radio galaxies. Our XMM observations show evidence that the GPS galaxies are heavily obscured with the large absorbing columns exceeding N(H)greater than le22 cm^-2. Taking into account the obscuration we determined that the intrinsic X-ray luminosities of GPS galaxies are of order le43-le44 erg/s, comparable to low luminosity radio loud quasars. The large GPS samples can confirm the result, as at this moment our evidence is based only on 7 GPS galaxies observed with good S/N/ in X-rays. The first paper summarizing the results of the XMM observation of Mkn 668 has been published Astronomy & Astrophysics. We found soft X-ray signatures of a hot plasma (kT approximately 10^7~K) and a hard X-ray emission from the nucleus. The X-ray spectrum above 2.5-keV is characterized by a very flat (observed photon index, Gamma-0.5) power-law continuum, alongside with a strong Fe-K-alpha neutral iron fluorescent line (EW~600-eV). The best explanation for the origin of this high energy X-ray emission is in terms of the Compton-reflection of the nuclear emission. The primary X-ray emission is obscured by a Compton-thick (N_H ~ to 10^24 ~cm-2) matter which becomes transparent at higher energies. The observed above 2.5-keV X-rays are mostly due to reflection which is indicated by a strong Fe-K-alpha line. This source represented the second hard X-ray detection of the GPS galaxy ever (the first one being 1345+125; O'Dea et al. 2000). The observations of the other GPS galaxies in our sample confirmed the trend of the large obscuration present in the spectra. However, we do not have a compelling evidence for a hot gas in the nucleus. The two other GPS galaxies observed with Chandra were added to the total of 7 GPS galaxies. This GPS sample was compared against the sample of radio loud galaxies and quasar. The paper is about to be submitted. Our preliminarily results based on the XMM-Newton data for the entire sample were presented at the meeting in July 2004.

Mushotsky, Richard↗

NASA NTRS2015

Testing Secondary Models for the Origin of Radio Mini-Halos in Galaxy Clusters

We present an MHD simulation of the emergence of a radio minihalo in a galaxy cluster core in a "secondary" model, where the source of the synchrotron-emitting electrons is hadronic interactions between cosmic-ray protons with the thermal intracluster gas, an alternative to the "reacceleration model" where the cosmic ray electrons are reaccelerated by turbulence induced by core sloshing, which we discussed in an earlier work. We follow the evolution of cosmic-ray electron spectra and their radio emission using passive tracer particles, taking into account the time-dependent injection of electrons from hadronic interactions and their energy losses. We find that secondary electrons in a sloshing cluster core can generate diffuse synchrotron emission with luminosity and extent similar to observed radio minihalos. However, we also find important differences with our previous work. We find that the drop in radio emission at cold fronts is less prominent than that in our reacceleration-based simulations, indicating that in this flavor of the secondary model the emission is more spatially extended than in some observed minihalos. We also explore the effect of rapid changes in the magnetic field on the radio spectrum. While the resulting spectra in some regions are steeper than expected from stationary conditions, the change is marginal, with differences in the synchrotron spectral index of delta(spectral index) less than approximately 0.15-0.25, depending on the frequency band. This is a much narrower range than claimed in the best-observed minihalos and produced in the reacceleration model. Our results provide important suggestions to constrain these models with future observations.

clusters: general aEuro" magnetohydrodynamics (MHD↗

DOE OSTI2017

The lightcone bootstrap and the spectrum of the 3d Ising CFT

In this paper. we compute numerically the dimensions and OPE coefficients of several operators in the 3d Ising CFT, and then try to reverse-engineer the solution to crossing symmetry analytically. Our key tool is a set of new techniques for computing infinite sums of SL(2,R) conformal blocks. Using these techniques, we solve the lightcone bootstrap to all orders in an asymptotic expansion in large spin, and suggest a strategy for going beyond the large spin limit. We carry out the first steps of this strategy for the 3d Ising CFT, deriving analytic approximations for the dimensions and OPE coefficients of several infinite families of operators in terms of the initial data $\{\Delta_\sigma,\Delta_\epsilon,f_{\sigma\sigma\epsilon},f_{\epsilon\epsilon\epsilon},c_T\}$. The analytic results agree with numerics to high precision for about 100 low-twist operators (correctly accounting for O(1) mixing effects between large-spin families). Plugging these results back into the crossing equations, we obtain approximate analytic constraints on the initial data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

DOE OSTI2021

A Markov framework for generalized post-event systems recovery modeling: From single to multihazards

State-dependent models can be used to represent the system recovery process as a series of stochastic transitions from lower to higher functional states. However, the applications of these models have been limited in scope and there is a lack of a generalized recovery modeling framework. A generalized framework would permit a robust forecasting of systems and system-of-systems recovery under multiple hazards, and more broadly, would contribute to community disaster preparedness. This paper develops a generalized post hazard-event recovery modeling framework based on state-dependent Markov-type processes. We then apply the proposed framework to solve a spectrum of problems that range from hind-casting single-system recovery following a single hazard event to forecasting post-event trajectories under multiple hazards and modeling the recovery of a system-of-systems. First, Markov chains are used to hind-cast the observed recovery for a portfolio of buildings affected by the 2014 South Napa, California, earthquake. Next, Markov processes are used to formulate a parametric post hazard-event recovery model, which can be updated using Bayesian statistics when relevant datasets become available. Semi-Markov processes are then used to develop a more general model of single hazard recovery, which accounts for the intensity of the loading and level of damage caused by the event. Semi-Markov processes with non-renewal features are then used to account for multihazard interactions in a post-event recovery model, and applied to a case study that involves a community in Charleston, South Carolina. Lastly, Markov-type processes are combined with Bayesian networks to model the recovery of residential, commercial, educational, and industrial buildings (system-of-systems) following a hazard event. Overall, these applications demonstrate the versatility of the Markov framework towards handling recovery problems with varying levels of complexity.

42 ENGINEERING↗

DOE OSTI2022

Electronic Spectroscopy and Dissociation Dynamics of Vinyl-Substituted Criegee Intermediates: 2-Butenal Oxide and Comparison with Methyl Vinyl Ketone Oxide and Methacrolein Oxide Isomers

The 2-butenal oxide Criegee intermediate [(CH 3 CH=CH)CHOO], an isomer of the four-carbon unsaturated Criegee intermediates derived from isoprene ozonolysis, is characterized on its first π * ←π electronic transition and by the resultant dissociation dynamics to O ( 1 D) + 2-butenal [(CH 3 CH=CH)CHO] products. The electronic spectrum of 2-butenal oxide under jet-cooled conditions is observed to be broad and unstructured with peak absorption at 373 nm, spanning to half maxima at 320 and 420 nm, and in good accord with the computed vertical excitation energies and absorption spectra obtained for its lowest energy conformers. The distribution of total kinetic energy released to products is ascertained through velocity map imaging of the O ( 1 D) products. About half of the available energy, deduced from the theoretically computed asymptotic energy, is accommodated as internal excitation of the 2-butenal fragment. A reduced impulsive model is introduced to interpret the photodissociation dynamics, which accounts for the geometric changes between 2-butenal oxide and the 2-butenal fragment, and vibrational activation of associated modes in the 2-butenal product. Application of the reduced impulsive model to the photodissociation of isomeric methyl vinyl ketone oxide reveals greater internal activation of the methyl vinyl ketone product arising from methyl internal rotation and rock, which is distinctly different than the dissociation dynamics of 2-butenal oxide or methacrolein oxide.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗