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At least 91 records · Page 5

Chemistry and Evolution of Interstellar Clouds

In this chapter we describe how elements have been and are still being formed in the galaxy and how they are transformed into the reservoir of materials present at the time of formation of our protosolar nebula. We discuss the global cycle of matter, beginning at its formation site in stars, where it is ejected through winds and explosions into the diffuse interstellar medium. In the next stage of the global cycle occurs in cold, dense molecular clouds, where the complexity of molecules and ices increases relative to the diffuse ISM.. When a protostar forms in a dense core within a molecular cloud, it heats the surrounding infalling matter warms and releases molecules from the solid phase into the gas phase in a warm, dense core, sponsoring a rich gas-phase chemistry. Some material from the cold and warm regions within molecular clouds probably survives as interstellar matter in the protostellar disk. For the diffuse ISM, for cold, dense clouds, and for dense-warm cores, the physio-chemical processes that occur within the gas and solid phases are discussed in detail.

Wooden, D. H.↗

Laboratory Astrophysics: The Universe in the Palm of Your Hand

Polycyclic aromatic compounds (PACs), a class of organic molecules whose structures are characterized by the presence of two or more fused aromatic rings, have been the subject of astrophysical interest for nearly two decades. Large by interstellar standards (from as few as 20 to perhaps as many as several hundred atoms), it has been suggested that these species are among the most abundant interstellar molecules impacting a wide range of astrophysical phenomena including: (1) the ubiquitous family of infrared emission bands observed in an ever-increasing assortment of astronomical objects; (2) the subtle but rich array of discrete visible/near-infrared interstellar molecular absorption features known as the diffuse interstellar bands (DIBs); (3) the broad near-infrared quasi-continuum observed in a number of nebulae known as excess red emission (ERE); (4) the interstellar ultraviolet extinction curve and broad '2200 Angstrom bump'; and (5) the heating/cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of good-quality laboratory spectroscopic data on PACs under astrophysically relevant conditions (i.e. isolated, ionized molecules, ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model. Fortunately, the last decade has seen an explosion of experimental and theoretical techniques aimed specifically at addressing these issues. Indeed, many of these techniques will be explored in the series of talks which constitute this forum. This talk will provide an overview of the studies of the spectroscopic properties of isolated, neutral, and ionized PACs that have been conducted in the Astrochemistry Laboratory at NASA Ames, together with a consideration of their implications for astrophysics. Particular attention will be paid to models of the interstellar infrared emission spectra generated using the available database of laboratory PAC infrared spectra and the natural ability of this database to accommodate the variations observed in the astronomical spectra. Such models provide insight into the structure, abundance, and ionization state of the interstellar PAC population and, in turn, provide direct insight into the processes of carbon nucleation, growth and evolution as matter is processed through the interstellar medium. These models will be followed by a more in depth look at some specific aspects of the interstellar infrared emission spectrum, considering both what we can learn about them and what we can learn from them. Finally, some of the limitations of the current model and the available spectroscopic dataset will be 'dered along with future experimental directions designed to address these shortcomings. Further information about this and the related areas of research currently ongoing in the Astrochemistry Laboratory can be found at our world wide web site. http://www-space.arc.nasa.gov/(tilda)astrochem

Hudgins, Douglas M.↗

Vibrational Spectroscopy at Cryogenic Temperatures: From the Laboratory to the Ends of the Universe

Polycyclic aromatic compounds (PAC) have been the subject of astrophysical interest for nearly two decades. Indeed, there is now evidence that these compounds are among the most abundant interstellar molecules, comprising perhaps 10 - 30% of all the carbon in our galaxy. Ranging in size from as few as 20 to as many as hundreds or thousands of carbon atoms, these molecules are enormous by interstellar standards and impact a wide range of astrophysical phenomena including: the near- and mid-infrared emission spectrum of a wide range of astronomical objects; the ultraviolet/visible/near-infrared absorption of the diffuse medium that permeates our galaxy; and the heating and cooling mechanisms of interstellar clouds. Nevertheless, until recently a lack of laboratory spectroscopic data on PAC under astrophysically relevant conditions (i.e. isolated, ionized molecules; ionized molecular clusters, etc.) has hindered critical evaluation and extension of this model. Fortunately, the last decade has seen an explosion of experimental and theoretical techniques aimed specifically at addressing these issues. Here, we begin with a brief review of the evidence for the existence and abundance of interstellar PAC. From there, we move on to an overview of the general spectroscopic characteristics of the range of isolated, neutral and ionized PAC that we have studied over the last decade. Finally, we will conclude with a consideration of the astrophysical implications and applications of interstellar PAC. Our discussion will revolve primarily around the observed interstellar infrared emission spectra and the ability of the laboratory spectra of varying combinations of PAC to accommodate both the global appearance and the region-to-region variability of this emission. Careful models based on sound laboratory spectroscopic data such as these now have the potential to provide insight into the structure, abundance, and ionization state of the interstellar PAC population. That, in turn, will provide direct insight into the processes of carbon nucleation, growth and evolution as matter is processed through the interstellar medium.

Hudgins, Douglas M.↗

Robust Optimization Design Algorithm for High-Frequency TWTs

Traveling-wave tubes (TWTs), such as the Ka-band (26-GHz) model recently developed for the Lunar Reconnaissance Orbiter, are essential as communication amplifiers in spacecraft for virtually all near- and deep-space missions. This innovation is a computational design algorithm that, for the first time, optimizes the efficiency and output power of a TWT while taking into account the effects of dimensional tolerance variations. Because they are primary power consumers and power generation is very expensive in space, much effort has been exerted over the last 30 years to increase the power efficiency of TWTs. However, at frequencies higher than about 60 GHz, efficiencies of TWTs are still quite low. A major reason is that at higher frequencies, dimensional tolerance variations from conventional micromachining techniques become relatively large with respect to the circuit dimensions. When this is the case, conventional design- optimization procedures, which ignore dimensional variations, provide inaccurate designs for which the actual amplifier performance substantially under-performs that of the design. Thus, this new, robust TWT optimization design algorithm was created to take account of and ameliorate the deleterious effects of dimensional variations and to increase efficiency, power, and yield of high-frequency TWTs. This design algorithm can help extend the use of TWTs into the terahertz frequency regime of 300-3000 GHz. Currently, these frequencies are under-utilized because of the lack of efficient amplifiers, thus this regime is known as the "terahertz gap." The development of an efficient terahertz TWT amplifier could enable breakthrough applications in space science molecular spectroscopy, remote sensing, nondestructive testing, high-resolution "through-the-wall" imaging, biomedical imaging, and detection of explosives and toxic biochemical agents.

Wilson, Jeffrey D.↗

Detection of explosives, nerve agents, and illicit substances by zero-energy electron attachment

The Reversal Electron Attachment Detection (READ) method, developed at JPL/Caltech, has been used to detect a variety of substances which have electron-attachment resonances at low and intermediate electron energies. In the case of zero-energy resonances, the cross section (hence attachment probability and instrument sensitivity) is mediated by the so-called s-wave phenomenon, in which the cross sections vary as the inverse of the electron velocity. Hence this is, in the limit of zero electron energy or velocity, one of the rare cases in atomic and molecular physics where one carries out detection via infinite cross sections.

vapor detection explosives electron detachment↗

High-Fidelity Mock Development for the Insensitive High Explosive TATB

Due to the violent reaction potential of high explosives, in tests where a reaction is not desired, it can be safe and convenient to use an inert mock that can mimic relevant properties of the associated explosive. Use of mock materials is well-established in explosives work, but most existing mocks are generally meant to mimic only one or two properties of a given explosive, potentially failing to match the explosive in other critical ways. Recently, there has been interest in developing robust thermomechanical mocks for many common explosives. Here, eleven materials are systematically chosen and investigated as potential thermomechanical mocks for TATB, the explosive component of PBX 9502. DSC, nanoindentation, and compression testing are used to narrow down to most appropriate mocks and identify their advantages and limitations. Hardness and elastic modulus are reported for the first time for the molecular crystals iodoanthranilic acid, hexamine, melamine, and trithiolane dioxide, and the crystal structure is reported for the first time for the molecular crystals iodoanthranilic acid and iodosalicylic acid.

36 MATERIALS SCIENCE↗

Impact of environmental oxygen on nanoparticle formation and agglomeration in aluminum laser ablation plumes

Here, the role of ambient oxygen gas (O 2 ) on molecular and nanoparticle formation and agglomeration was studied in laser ablation plumes. As a lab-scale surrogate to a high explosion detonation event, nanosecond laser ablation of an aluminum alloy (AA6061) target was performed in atmospheric pressure conditions. Optical emission spectroscopy and two mass spectrometry techniques were used to monitor the early to late stages of plasma generation to track the evolution of atoms, molecules, clusters, nanoparticles, and agglomerates. The experiments were performed under atmospheric pressure air, atmospheric pressure nitrogen, and 20% and 5% O 2 (balance N 2 ), the latter specifically with in situ mass spectrometry. Electron microscopy was performed ex situ to identify crystal structure and elemental distributions in individual nanoparticles. We find that the presence of ≈20% O 2 leads to strong AlO emission, whereas in a flowing N 2 environment (with trace O 2 ), AlN and strong, unreacted Al emissions are present. In situ mass spectrometry reveals that as O 2 availability increases, Al oxide cluster size increases. Nanoparticle agglomerates formed in air are found to be larger than those formed under N 2 gas. High-resolution transmission electron microscopy demonstrates that Al 2 O 3 and AlN nanoparticle agglomerates are formed in both environments; indicating that the presence of trace O 2 can lead to Al 2 O 3 nanoparticle formation. The present results highlight that the availability of O 2 in the ambient gas significantly impacts spectral signatures, cluster size, and nanoparticle agglomeration behavior. These results are relevant to understanding debris formation in an explosion event, and interpreting data from forensic investigations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

On the calculation of turbulent heat transport downstream from an abrupt pipe expansion

A numerical study of flow and heat transfer in the separated flow region produced by an abrupt pipe explosion is reported, with emphasis on the region in the immediate vicinity of the wall where turbulent transport gives way to molecular conduction and diffusion. The analysis is based on a modified TEACH-2E program with the standard k-epsilon model of turbulence. Predictions of the experimental data of Zemanick and Dougall (1970) for a diameter ratio of 0.54 show generally encouraging agreement with experiment. At a diameter ratio of 0.43 different trends are discernable between measurement and calculation, though this appears to be due to effects unconnected with the wall region studied here.

Chieng, C. C.↗

The Good, the Bad, and the Ugly: Pseudopotential Inconsistency Errors in Molecular Applications of Density Functional Theory

The pseudopotential (PP) approximation is one of the most common techniques in computational chemistry. Despite its long history, the development of custom PPs has not tracked with the explosion of different density functional approximations (DFAs). As a result, the use of PPs with exchange/correlation models for which they were not developed is widespread, although this practice is known to be theoretically unsound. The extent of PP inconsistency errors (PPIEs) associated with this practice has not been systematically explored across the types of energy differences commonly evaluated in chemical applications. Here, we evaluate PPIEs for a number of PPs and DFAs across 196 chemically relevant systems of both transition-metal and main-group elements, as represented by the W4-11, TMC34, and S22 data sets. Near the complete basis set limit, these PPs are found to cleanly approach all-electron (AE) results for noncovalent interactions but introduce root-mean-squared errors (RMSEs) upwards of 15 kcal mol –1 into predictions of covalent bond energies for a number of popular DFAs. We achieve significant improvements through the use of empirical atom- and DFA-specific PP corrections, indicating considerable systematicity of the PPIEs. The results of this work have implications for chemical modeling in both molecular contexts and for DFA design, which we discuss.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two-Dimensional Projected-Momentum Covariance Mapping for Coulomb Explosion Imaging

We introduce projected-momentum covariance mapping, an extension of recoil-frame covariance mapping for 2D ion imaging studies. By considering the two-dimensional projection of the ion momenta as recorded by the detector, one opens the door to a complex suite of analysis tools adapted from three-dimensional momentum imaging studies. This includes the use of different frames of reference to unravel the dynamics of fragmentation and the application of fragment momentum constraints to isolate specific fragmentation channels. The technique is demonstrated on data from a two-dimensional ion imaging study of the Coulomb explosion of the cis and trans isomers of 1,2-dichloroethene, following strong-field ionization by an intense near-infrared femtosecond laser pulse. Classical simulations are used to guide the interpretation of projected-momentum covariance maps. The results offer a detailed insight into the distinct Coulomb explosion dynamics for this pair of isomers and lay the groundwork for future time-resolved studies of photoisomerization dynamics in this molecular system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Anisotropic strength behavior of single-crystal TATB

High-rate strength behavior plays an important role in the shock initiation of high explosives, with plastic deformation serving to localize heat into hot spots and as a mechanochemical means to enhance reactivity. Recent simulations predict that detonation-like shocks produce highly reactive nanoscale shear bands in the layered crystalline explosive TATB (1,3,5-triamino-2,4,6-trinitrobenzene), but the thresholds leading to this response are poorly understood. We utilize molecular dynamics to simulate the high-rate compressive stress–strain response of TATB, with a focus on understanding flow behavior. Here, the dependence of strength on pressure and loading axis (crystal orientation) is explored. The deformation mechanisms fall broadly into two categories, with compression along crystal layers activating a buckling/twinning mode and compression normal to the layers producing nanoscale shear bands. Despite the complexity of the underlying mechanisms, the crystal exhibits relatively straightforward stress–strain curves. Most of the crystal orientations studied show rapid strain softening following the onset of yielding, which settles to a steady flow state. Trajectories are analyzed using five metrics for local states and structural order, but most of these metrics yield similar distributions for these deformation mechanisms. On the other hand, a recently proposed measure of intramolecular strain energy is found to most cleanly distinguish between these mechanisms, while also providing a plausible connection with mechanochemically accelerated decomposition kinetics. Localization of intramolecular strain energy is found to depend strongly on crystal orientation and pressure.

36 MATERIALS SCIENCE↗

Image Distinguishability Analysis Testing Through Principal Components and Its Application to Hot Spot Scale Invariance

Hot spots are spatial regions of intense energy localization that govern initiation of secondary high explosives. Studies that characterize or compare simulated hot spots are frequently either qualitatively descriptive or resort to quantitative distribution functions that neglect stochastic variations and spatial correlations—effects that are also neglected in common comparison tests like the Kolmogorov–Smirnov test. To this end, we develop an image distinguishability analysis (IDA) test based on principal component (PC) analysis that makes pixel-by-pixel comparisons between small, for example, O(<10), image data sets. The IDA test makes comparisons through a generalized distance metric in the PC space and a test statistic that is derived to calculate mathematical equation-values. Here, we derive a statistical distribution and criticality criterion to determine whether images are distinguishable from established baselines. We apply the IDA test on images generated from molecular dynamics simulations of hot spots from pore collapse in TATB to assess scale invariance in the complex patterns of hot spots that form in a representative high explosive crystal. The IDA test shows that TATB hot spot spatial temperature fields and their derived temperature histograms exhibit scale-invariant features over specific intervals of shock orientation, strength, and initial pore diameter. However, the IDA test also shows that qualitatively different conclusions regarding invariance can be reached depending on whether the hot spot is treated as a spatially correlated field as opposed to a distribution function that lacks spatial information.

organic↗

Radiolytic Gas Production from Aluminum Coupons (Alloy 1100 and 6061) in Helium Environments—Assessing the Extended Storage of Aluminum Clad Spent Nuclear Fuel

Corrosion of aluminium alloy clad nuclear fuel, during reactor operation and under subsequent wet storage conditions, promotes the formation of aluminium hydroxide and oxyhydroxide layers. These hydrated mineral phases and the chemisorbed and physisorbed waters on their surfaces are susceptible to radiation-induced processes that yield molecular hydrogen gas (H 2 ), which has the potential to complicate the long-term storage and disposal of aluminium clad nuclear fuel through flammable and explosive gas mixture formation, alloy embrittlement, and pressurization. Here, we present a systematic study of the radiolytic formation of H 2 from aluminium alloy 1100 (AA1100) and 6061 (AA6061) coupons in “dry” (~0% relative humidity) and “wet” (50% relative humidity) helium environments. Cobalt-60 gamma irradiation of both aluminium alloy types promoted the formation of H 2 , which increased linearly up to ~2 MGy, and afforded G-values of 1.1 ± 0.1 and 2.9 ± 0.1 for “dry” and “wet” AA1100, and 2.7 ± 0.1 and 1.7 ± 0.1 for “dry” and “wet” AA6061. The negative correlation of H 2 production with relative humidity for AA6061 is in stark contrast to AA1100 and is attributed to differences in the extent of corrosion and varying amounts of adsorbed water in the two alloys, as characterized using optical profilometry, scanning electron microscopy, Raman spectroscopy, and X-ray diffraction techniques.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Imaging multiphoton ionization dynamics of CH 3 I at a high repetition rate XUV free-electron laser

XUV multiphoton ionization of molecules is commonly used in free-electron laser experiments to study charge transfer dynamics. However, molecular dissociation and electron dynamics, such as multiple photon absorption, Auger decay, and charge transfer, often happen on competing time scales, and the contributions of individual processes can be difficult to unravel. We experimentally investigate the Coulomb explosion dynamics of methyl iodide upon core–hole ionization of the shallow inner-shell of iodine (4d) and classically simulate the fragmentation by phenomenologically introducing ionization dynamics and charge transfer. Under our experimental conditions with medium fluence and relatively long XUV pulses (~75 fs), we find that fast Auger decay prior to charge transfer significantly contributes to the charging mechanism, leading to a yield enhancement of higher carbon charge states upon molecular dissociation. Furthermore, we argue for the existence of another charging mechanism for the weak fragmentation channels leading to triply charged carbon atoms. This study shows that classical simulations can be a useful tool to guide the quantum mechanical description of the femtosecond dynamics upon multiphoton absorption in molecular systems.

Optics↗

Predicting Energetics Materials’ Crystalline Density from Chemical Structure by Machine Learning

To expedite new molecular compound development, a long-sought goal within the chemistry community has been to predict molecules’ bulk properties of interest a priori to synthesis from a chemical structure alone. In this work, we demonstrate that machine learning methods can indeed be used to directly learn the relationship between chemical structures and bulk crystalline properties of molecules, even in the absence of any crystal structure information or quantum mechanical calculations. We focus specifically on a class of organic compounds categorized as energetic materials called high explosives (HE) and predicting their crystalline density. An ongoing challenge within the chemistry machine learning community is deciding how best to featurize molecules as inputs into machine learning models—whether expert handcrafted features or learned molecular representations via graph-based neural network models—yield better results and why. We evaluate both types of representations in combination with a number of machine learning models to predict the crystalline densities of HE-like molecules curated from the Cambridge Structural Database, and we report the performance and pros and cons of our methods. Our message passing neural network (MPNN) based models with learned molecular representations generally perform best, outperforming current state-of-the-art methods at predicting crystalline density and performing well even when testing on a data set not representative of the training data. However, these models are traditionally considered black boxes and less easily interpretable. Here, to address this common challenge, we also provide a comparison analysis between our MPNN-based model and models with fixed feature representations that provides insights as to what features are learned by the MPNN to accurately predict density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The bird: A pressure-confined explosion in the interstellar medium

The non-thermal radio continuum source G5.3-1.0, mapped at 20 cm with the Very Large Array (VLA) by Becker and Helfand, has an unusual bird-like shape. In order to determine possible interaction of this source with adjacent cold gas, we have mapped this region in the J=1-0 line of CO using the AT and T Bell Laboratories 7m antenna and the FCRAO 14m antenna. The map shown contains 1859 spectra sampled on a 1.5 arcminute grid; each spectrum has an rms noise of 0.2 K in 1 MHz channels. There are several molecular clouds at different velocities along the line of sight. The outer regions of a previously unknown Giant Molecular Cloud (GMC) at l=4.7 deg., b=-0.85 deg., v=200 km s(-1) appears to be interacting with G5.3-10: the molecular cloud has a bird-shaped hole at the position of the continuum source, except that the brightest continuum point (the bird's head) appears to be embedded in the cloud. The velocity of this GMC indicates it is within 2 kpc of the galactic center. The morphology suggests that a supernova or other explosive event occurred near the outside of the GMC, in a region where (n) is approximately 300 cm(-3), and expanded into a region of lower density and pressure. The pressures, densities, and velocity gradients of molecular clouds near the galactic center are on average higher than those of clouds near the Sun. We therefore expect that Type II supernovae near the galactic center would be distorted by their interactions with their parent molecular clouds.

Lane, A. P.↗

Ionization of interstellar H2 clouds by supernovae

Two destruction mechanisms for molecular hydrogen in the H I regions of the interstellar medium were given by Stecher and Williams (1967). The first is dominant in weak radiation fields and involves photon excitation (at about 1000 A) to the first excited electronic state with a subsequent decay into the vibrational continuum of the ground state. The second destruction mechanism is dominant in the strong photon fields that exist when a supernova explosion occurs. It involves photoionization (at about 1000 A) from metastable high vibrational levels produced by photon excitation (in the same wavelength range) to an excited electronic state and subsequent decay to bound vibrational levels. It is shown that ionization of molecular hydrogen can occur at considerable distances from such supernova events while the atomic hydrogen remains neutral. The effect should be observable in the dispersion measures of new pulsars.

Stecher, T. P.↗

Identification of Suitable Vacuum Gas Oils as Plasticizers Using HT-GC × GC-HRMS

Vacuum gas oils (VGOs) have long been heralded as effective plasticizers due to their high boiling-points and lubricating properties. One of these VGOs, HyVac Oil 93050, is a paraffinic plasticizer that is currently utilized in polymer–plasticizer explosive formulations, while this oil effectively increases the elasticity and decreases the sensitivity for current formulations. We seek to identify alternative VGOs with similar density, viscosity, molecular composition, and impurities for future formulations. In this study, 18 VGOs, including HyVac Oil 93050, were initially evaluated for their density and viscosity. The oils were then ranked based on physical characteristics and analyzed for molecular composition using high-temperature comprehensive two-dimensional gas chromatography with high-resolution time-of-flight mass spectrometry (HT-GC × GC-HRMS). Further, the HT-GC × GC-HRMS chromatograms of the top 10 most similar VGOs to HyVac Oil 93050, according to density, were compared utilizing the Pearson correlation coefficient. Three of the oils with densities similar to those of HyVac Oil 93050 had a Pearson correlation within the lot-to-lot variation of HyVac Oil 93050. For the top 3 candidates, Pearson correlation was then utilized as a feature selection technique to discover significant chemical differences. Positive chemical ionization (PCI) and negative chemical ionization (NCI) HT-GC × GC-HRMS chromatograms were also evaluated and aided in the discovery and identification of several key compounds including additives that acted as stabilizers for the VGOs. After this further chemical analysis, two of the original 17 potential VGOs were determined to be physically and chemically similar to HyVac Oil 93050.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗