Dissociative excitation of vacuum ultraviolet emission features by electron impact on molecular gases. III - CO2.
Abstract missing.
Mumma, M. J.↗
SEARCH · Engineering Papers
Results for “MOLECULAR DISSOCIATION”
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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Dissociation energy and vibrational terms of ground state /X /1 Sigma g plus// hydrogen
Computations of binding energies and vibrational energies of ground state molecular hydrogen to measure accuracy of dissociation energy
Bernstein, R. B.↗
Imaging Three-Dimensional Molecular Structure and Dynamics with Multiparticle Covariance and Cumulant Coulomb Explosion Analysis
Coulomb explosion imaging (CEI) provides a direct means of imaging molecular geometry by correlating fragment ion momenta following the fragmentation of a molecular polycation. Here, we demonstrate the use of three-body covariance and four-body cumulant analysis to extract three-dimensional (3D) structural information from the X-ray-induced Coulomb explosion of tert-butyl iodide (C4H9I). Site-selective ionization at the iodine 4d edge with intense femtosecond soft X-ray pulses from an X-ray free-electron laser (XFEL) enables rapid charge buildup and molecular breakup. By correlating ionic fragments in the molecular frame, we isolate complete dissociation channels and reveal subtle structural changes, such as umbrella-type motion of the branched alkyl chain, during the ionization process. Comparison with point-charge simulations of the Coulomb explosion shows close agreement, validating the approach. Furthermore, these results establish covariance/cumulant mapping as a powerful strategy for imaging complex three-dimensional molecular structures and point the way toward time-resolved CEI using both XFEL and tabletop sources for capturing ultrafast structural dynamics.
Imaging↗
Understanding Hydrogenation Chemistry at MgB 2 Reactive Edges from Ab Initio Molecular Dynamics
Solid-state hydrogen storage materials often operate via transient, multistep chemical reactions at complex interfaces that are difficult to capture. Here, we use direct ab initio molecular dynamics simulations at accelerated temperatures and hydrogen pressures to probe the hydrogenation chemistry of the candidate material MgB 2 without a priori assumption of reaction pathways. Focusing on highly reactive ($10\overline{1}0$) edge planes where initial hydrogen attack is likely to occur, we track mechanistic steps toward the formation of hydrogen-saturated BH 4 – units and key chemical intermediates, involving H 2 dissociation, generation of functionalities and molecular complexes containing BH 2 and BH 3 motifs, and B–B bond breaking. Further, the genesis of higher-order boron clustering is also observed. Different charge states and chemical environments at the B-rich and Mg-rich edge planes are found to produce different chemical pathways and preferred speciation, with implications for overall hydrogenation kinetics. The reaction processes rely on B–H bond polarization and fluctuations between ionic and covalent character, which are critically enabled by the presence of Mg 2+ cations in the nearby interphase region. Our results provide guidance for devising kinetic improvement strategies for MgB 2 -based hydrogen storage materials, while also providing a template for exploring chemical pathways in other solid-state energy storage reactions.
08 HYDROGEN↗
Conversion of laser energy to gas kinetic energy
Techniques for the gas phase absorption of laser radiation for conversion to gas kinetic energy are discussed. Absorption by inverse Bremsstrahlung, in which laser energy is converted at a gas kinetic rate in a spectrally continuous process, is briefly described, and absorption by molecular vibrational rotation bands is discussed at length. High pressure absorption is proposed as a means of minimizing gas bleaching and dissociation, the major disadvantages of the molecular absorption process. A band model is presented for predicting the molecular absorption spectra in the high pressure absorption region and is applied to the CO molecule. Use of a rare gas seeded with Fe(CO)5 for converting vibrational modes to translation modes is described.
Caledonia, G. E.↗
Plasma decay in hydrocarbons and hydrocarbon- and H 2 O-containing mixtures excited by high-voltage nanosecond discharge at elevated gas temperatures
Plasma decay after a high-voltage nanosecond discharge was experimentally and numerically studied in pure hydrocarbons (C 2 H 6 and C 3 H 8 ), and H 2 O:N 2 and C 3 H 8 :O 2 mixtures for pressures in the range 2–4 Torr and gas temperatures from 300 to 600 K. In a stoichiometric C 3 H 8 :O 2 mixture, plasma decay was also studied in a repetitively pulsed discharge for varing numbers of discharge pulses (varying degrees of fuel oxidation). The rate of plasma decay was determined from the temporal evolution of electron density measured using the microwave interferometer. It was observed that gas heating to 600 K leads to a decrease in the rate of plasma decay in all cases. The effect of heating on plasma decay was most profound in the H 2 O:N 2 mixture (after a single discharge pulse) and in the C 3 H 8 :O 2 mixture for high degrees of fuel oxidation. A kinetic scheme was developed to numerically simulate the plasma decay in hydrocarbons and combustible mixtures. Numerical analysis showed that, under the conditions studied, plasma decay was controlled by dissociative electron recombination with simple molecular and cluster ions. Gas heating led to a decrease in the rate of the electron-ion recombination and the rate of conversion of molecular ions to cluster ions. As a result, the gas temperature increase caused a decrease in the fraction of cluster ions for which the recombination coefficients are an order of magnitude higher than the recombination coefficients for molecular ions. The influence of gas heating on the decrease of the amount of cluster ions was more important when the ion composition was dominated by hydrated H 3 O + (H 2 O) k ions. The rates of the formation of these ions are extremely sensitive to any variations in gas temperature. A result, in agreement with our observations, gas heating led to an anomalous decrease in the rates of plasma decay in the H 2 O:N 2 mixture, as well as in the C 3 H 8 :O 2 mixture when H 2 O molecules were produced due to fuel oxidation.
20 FOSSIL-FUELED POWER PLANTS↗
The Search for New Molecular Species in the Atmosphere of Titan
The atmosphere of Saturn’s moon, Titan, contains a vast array of minor molecular constituents originating from the dissociation of its primary compounds, N2and CH4. The extent of Titan’s photochemical network was revealed by ionospheric measurements from the Cassini orbiter, leaving substantial gaps in the corresponding neutral inventory typically probed through infrared spectroscopy. Utilizing the unprecedented sensitivity and high spectral resolution of the Atacama Large Millimeter/submillimeter Array (ALMA) at longer wavelengths, we searched for additional trace gases in Titan’s atmosphere during 2016, 2017,and 2019to further characterize Titan’s atmospheric and surface composition. These observations have resulted in the spectroscopic detections of the small cyclic molecule, cyclopropenylidene (c-C3H2), and the largest nitrile to date, methyl cyanoacetylene (CH3C3N), for the first time in Titan’s atmosphere –or anywhere else in the Solar System. We employed radiative transfer models to determine the volume mixing ratio of both species in Titan’s middle and upper atmosphere (altitudes > 350 km)and constrained the total column densities for the incorporation into future photochemical models of Titan’s atmosphere. Discrepancies between these results and current models necessitates the need for dedicated laboratory and modeling studies regarding the production pathways for trace complex organics in Titan’s atmosphere. Additionally, the measurement of previously undetected molecular species provides further incentive for the study of planetary atmospheres in the (sub)millimeter regime with facilities such as ALMA.
A E Thelen↗
Radiation enhanced dissociation of hydrogen in nuclear rockets
The effect of radiation-induced dissociation of hydrogen gas in nuclear rockets is studied. The dissociation degree is obtained by solving rate equations, which include the fast-ion induced dissociation and ionization of atomic and molecular hydrogens. Analytical formulas are used to estimate a change in the viscosity and the specific impulse. It was found that the fast-ion induced dissociation plays an important role in enhancing the specific impulse for nuclear rocket concepts using hydrogen gas at low pressures (less than 0.1 MPa) and low temperatures (less than 3000 K). It is also shown that the specific impulse is enhanced by mixing helium-3, lithium-6, boron-10, or uranium-235 with hydrogen.
Watanabe, Yoichi↗
Super‐Hydrophilic Microporous Ni(OH) x /Ni 3 S 2 Heterostructure Electrocatalyst for Large‐Current‐Density Hydrogen Evolution
Abstract Exploiting active and stable non‐precious metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at large current density plays a key role in realizing large‐scale industrial hydrogen generation. Herein, a self‐supported microporous Ni(OH) x /Ni 3 S 2 heterostructure electrocatalyst on nickel foam (Ni(OH) x /Ni 3 S 2 /NF) that possesses super‐hydrophilic property through an electrochemical process is rationally designed and fabricated. Benefiting from the super‐hydrophilic property, microporous feature, and self‐supported structure, the electrocatalyst exhibits an exceptional HER performance at large current density in 1.0 M KOH, only requiring low overpotential of 126, 193, and 238 mV to reach a current density of 100, 500, and 1000 mA cm −2 , respectively, and displaying a long‐term durability up to 1000 h, which is among the state‐of‐the‐art non‐precious metal electrocatalysts. Combining hard X‐rays absorption spectroscopy and first‐principles calculation, it also reveals that the strong electronic coupling at the interface of the heterostructure facilitates the dissociation of H 2 O molecular, accelerating the HER kinetics in alkaline electrolyte. This work sheds a light on developing advanced non‐precious metal electrocatalysts for industrial hydrogen production by means of constructing a super‐hydrophilic microporous heterostructure.
Chemistry↗
Resolving SPARC–HSA binding kinetics with an ultrasensitive photonic sensor based on bound states in the continuum
Secreted protein acidic and rich in cysteine (SPARC) is critical in cell-matrix interactions and tissue remodeling. It influences tumor progression through its affinity for human serum albumin (HSA) - the most abundant plasma protein, which also plays a crucial role in drug delivery. Strong molecular binding leads to a dissociation constant KD in the nanomolar range. Thus, determining KD requires detecting sub-nanomolar concentrations with ultrasensitive methods. This may be crucial for elucidating the nature of SPARC-HSA binding, as their interaction remains a subject of debate. Capturing these interactions accurately requires a platform capable of resolving rapid binding kinetics at extremely low analyte concentrations. In this work, we report on a microfluidics-integrated photonic nanostructure that supports bound states in the continuum (BICs) and is optimized for studying the fast kinetics of high-affinity protein-protein interactions. The unprecedented capability of detecting sub-nanomolar concentrations allows quantifying KD between SPARC and HSA beyond the state of the art. We leverage an all-dielectric photonic crystal slab (PhCS) sustaining two BIC branches arising from gapped Dirac cone dispersion. HSA is covalently immobilized on the PhCS bonded to a PDMS microfluidic chamber. SPARC dissociation is carried out using PBS buffer (pH 7.4), ensuring complete protein release through precise control of the flow rate and continuous spectral monitoring of the BICs. The measured KD=8.2±0.8 nM confirms the strong affinity of SPARC for HSA. This study highlights the potential of BIC-based sensing as a versatile tool for investigating protein interactions. These results also have implications for the optimization of drug delivery systems and cancer treatment strategies.
Albumin↗
Studies of low-energy ionic collisions Final report, 1 Oct. 1965 - 30 Sep. 1967
Ionic-molecular collisions, and collision induced dissociation of ions
Bailey, T. L.↗
The equatorial airglow and the ionospheric geomagnetic anomaly
OGO D observations of OI (6300A) emissions reveal a global pattern in the equatorial airglow undetected from the ground-based observations. The post sunset emission rate of OI is generally asymmetrical with respect to the geomagnetic equator and shows no apparent correlation with the ultraviolet airglow (OI 1304 and 1356A) and F region electron density measured simultaneously from the same spacecraft. Both the ultraviolet airglow and the ion density measured in the altitude region of 450 km follow similar latitudinal variations and exhibit properties of the equatorial ionospheric anomaly. The asymmetry in OI emission can be attributed to the asymmetry in the height of the F 2 maximum inferred from the height of the maximum emission. From correlative studies of the airglow and the ionospheric measurements, the mechanisms for the ultraviolet and the 6300A emission are discussed in terms of the processes involving radiative and dissociative recombinations. A relationship between molecular oxygen density and the integrated OI emission rate is derived and the feasibility of using this relationship for estimating O2 density is discussed.
Chandra, S.↗
Mass and energy balance of the cold Io torus
A new model of the cold Io torus is described. Ions and energy are injected into the system by independent processes so that the mass balance is isolated from the energy balance. The primary source of energy is local ionization and acceleration of hot pickup ions resulting from charge exchange between thermal ions and an extended cloud of Iogenic sulfur and oxygen atoms. The primary energy loss mechanism of the plasma is collisionally excited line emission at optical wavelengths. The primary ion source is radial diffusion inward from the hot torus on a time scale of 140-710 days. The primary ion loss mechanism is a novel two-step enhanced recombination mechanism involving charge exchange between thermal ions and an extended cloud of neutral SO2 molecules, followed by rapid dissociative recombination of the resultant molecular ion. The model provides a self-consistent solution which reconciles a number of diverse observations with known physical processes.
Moreno, M. A.↗
Molecular line emission models of Herbig-Haro objects. I - H2 emission
A comprehensive model for molecular hydrogen emssion in Herbig-Haro objects that are associated with the heads of radiative stellar jets is presented by using a simple representation of the jet head as a comprising a leading bow shock and a trailing jet shock, separated by a dense layer of cool shocked gas. Attention is given to collisional excitation in a nondissociative shock and formation pumping in the molecular reformation zone behind a dissociative shock, employing detailed shock and photodissociation-region emission models that incorporate most of the relevant atomic physics and chemistry. The conditions under which each of these excitation mechanisms may be expected to contribute to the observed emission are discussed, and a general diagnostic scheme for discriminating among them is constructed. Applying this scheme to the HH 1-2 system, strong evidence for excitation by the radiation field of a fast shock is found. It is inferred that FUV pumping contributes a significant fraction of the H2 line emission, and it is shown that this can occur only if the UV pump lines are not strongly self-shielded.
Wolfire, Mark G.↗
Electronic excitation of ground state atoms by collision with heavy gas particles
Most of the important chemical reactions which occur in the very high temperature air produced around space vehicles as they enter the atmosphere were investigated both experimentally and theoretically, to some extent at least. One remaining reaction about which little is known, and which could be quite important at the extremely high temperatures that will be produced by the class of space vehicles now contemplated - such as the AOTV - is the excitation of bound electron states due to collisions between heavy gas particles. Rates of electronic excitation due to free electron collisions are known to be very rapid, but because these collisions quickly equilibrate the free and bound electron energy, the approach to full equilibrium with the heavy particle kinetic energy will depend primarily on the much slower process of bound electron excitation in heavy particle collisions and the subsequent rapid transfer to free electron energy. This may be the dominant mechanism leading to full equilibrium in the gas once the dissociation process has depleted the molecular states so the transfer between molecular vibrational energy and free electron energy is no longer available as a channel for equilibration of free electron and heavy particle kinetic energies. Two mechanisms seem probable in electronic excitation by heavy particle impact. One of these is the collision excitation and deexcitation of higher electronic states which are Rydberg like. A report, entitled 'Semi-Classical Theory of Electronic Excitation Rates', was submitted previously. This presented analytic expressions for the transition probabilities, assuming that the interaction potential is an exponential repulsion with a perturbation ripple due to the dipole-induced dipole effect in the case of neutral-neutral collisions, and to the ion-dipole interaction in the case of ion-neutral collisions. However the above may be, there is little doubt that excitation of ground state species by collision occurs at the point where the initial and final potentials cross, or at least come very close. Therefore, this mechanism would be applicable to the case where a gas is initially at very low temperature suddenly subjected to high energy heavy particle bombardment. This situation would model the measurement of excitation cross section by molecular beam techniques, for example. The purpose is to report values of cross sections and rate coefficients for collision excitation of ground state atoms estimated with the Landau-Zener transition theory and to compare results with measurement of excitation cross sections for a beam of Hydrogen atoms impacting Argon atom targets. Some very dubious approximations are used, and the comparison with measurement is found less than ideal, but results are at least consistent within order of magnitude. The same model is then applied to the case of N-N atom collisions, even though the approximations then become even more doubtful. Still the rate coefficients obtained are at least plausible in both magnitude and functional form, and as far as I am aware these are the only estimates available for such rate coefficients.
Hansen, C. Frederick↗
A Global Atmospheric Model of Meteoric Iron
The first global model of meteoric iron in the atmosphere (WACCM-Fe) has been developed by combining three components: the Whole Atmosphere Community Climate Model (WACCM), a description of the neutral and ion-molecule chemistry of iron in the mesosphere and lower thermosphere (MLT), and a treatment of the injection of meteoric constituents into the atmosphere. The iron chemistry treats seven neutral and four ionized iron containing species with 30 neutral and ion-molecule reactions. The meteoric input function (MIF), which describes the injection of Fe as a function of height, latitude, and day, is precalculated from an astronomical model coupled to a chemical meteoric ablation model (CABMOD). This newly developed WACCM-Fe model has been evaluated against a number of available ground-based lidar observations and performs well in simulating the mesospheric atomic Fe layer. The model reproduces the strong positive correlation of temperature and Fe density around the Fe layer peak and the large anticorrelation around 100 km. The diurnal tide has a significant effect in the middle of the layer, and the model also captures well the observed seasonal variations. However, the model overestimates the peak Fe+ concentration compared with the limited rocket-borne mass spectrometer data available, although good agreement on the ion layer underside can be obtained by adjusting the rate coefficients for dissociative recombination of Fe-molecular ions with electrons. Sensitivity experiments with the same chemistry in a 1-D model are used to highlight significant remaining uncertainties in reaction rate coefficients, and to explore the dependence of the total Fe abundance on the MIF and rate of vertical transport.
meteoric inputfunction↗
Gas Stopper Developments for Improved Purity and Intensity of Low-Energy, Rare Isotope Ion Beams (Final Technical Report)
This final technical report summarizes the work of the Michigan State University (MSU) team supported by grant # DE-SC0021423 awarded by the Office of Nuclear Physics, Department of Energy. Objectives: The successful fulfillment of the FRIB science mission hinges on ensuring the availability of fast, stopped, and reaccelerated beams consisting of rare isotopes. This project's research and development focus was dedicated to supporting the advancement and creation of a cutting-edge linear gas stopper. The primary aim is to efficiently convert the high-intensity fast beams of rare isotopes provided by FRIB into high-quality, low-energy beams. These beams are essential for conducting stopped beam experiments or for subsequent reacceleration. The overarching goal is to advance technology, aiming to increase the beam rate capability of the linear gas stopper for medium-to-heavy-mass rare isotopes by more than tenfold compared to the currently most effective gas stopper in operation, and to improve the purity of the delivered beams. Project Description: The existing technology employed in gas stopping devices designed for low-energy, rare-isotope beams presents limitations in both the purity of extracted beams and the intensities of injected beams. These limitations are incompatible with the requirements of the recently commissioned rare isotope beam facility, FRIB. Our research and development efforts, aligned with the previously outlined objectives, focused on addressing the most critical aspects for enhancing beam-rate capability and purity. Specifically, advanced particle-in-cell simulations were developed and integrated into a simulation pipeline to explore the efficacy of multi-layer RF carpets on increasing ion transport efficiency with high incoming beam rates that generate space charge fields which can limit it. We also explored the possibility of using a collision-induced-dissociation (CID) gas cell to break up molecular contaminant ions that are generated during the stopping process. A prototype CID gas cell was constructed and tested with beams from an offline ion source, validating the concept with the successful demonstration of breaking of molecular ions. The outcome of this research enabled the formulation a conceptual design for a next-generation linear gas stopping device specifically tailored for FRIB. This device is envisioned to deliver rare-isotope-ion beams at a rate of 10 8 particles per second or higher, accompanied by advancements in purity. Methods employed: This project leverages advancements in technologies initially designed for the Advanced Cryogenic Gas Stopper (ACGS), the current state-of-the-art linear gas stopper, through the use of new simulations and beam purification via collision-induced-dissociation. The methods include: 1. Development of a prototype low-energy, low-pressure CID gas stopper. This prototype features a thin, approximately 20 nm, Si 3 N 4 entrance window designed for dissociating stable and rare-isotope molecular ions. The goal is to enhance beam purification and overall efficiency. 2. Creation of Particle-in-cell (PIC) simulations to assess the advantages of multi-layer RF carpets and multi-point extraction for ion transport efficiency. These simulations rely on the 3DCylPIC package, specifically designed for studying devices of this nature. The goal is to quantify and mitigate ion transport losses due to space charge generated in the stopping process of large numbers of ions. 3. Perform ion transport simulations across an RF carpet using an 8-phase travelling wave and evaluate its performance. Compared to the 4-phase RF carpets used in ACGS, the 8-phase carpets will double the wavelength of the generated traveling wave allowing for larger maximum RF amplitudes that could result in improved ion transport efficiency for high-intensity incoming beams when large space charge fields are present. Impact: Tackling the primary challenges associated with transforming high-energy projectile fragment beams into low-energy beams—specifically, addressing efficiency and purity—holds significant promise for advancing FRIB science. This advancement will particularly impact precision mass measurements, laser spectroscopy of short-lived nuclei, and studies in astrophysics and nuclear reactions using reaccelerated beams. These domains play a crucial role in addressing key questions outlined in the 2023 NSAC long-range plan, spanning nuclear structure, nuclear astrophysics, and fundamental symmetries. Additionally, they contribute to addressing 10 out of the 17 benchmarks identified by the NRC RISAC. The development of a next-generation gas stopping device capable of delivering low-energy, rare-isotope beams at a rate of 10 8 particles per second, or more, with high purity holds the potential to unlock experiments that would otherwise be unfeasible. Furthermore, it is expected to reduce the time required for experiments at FRIB, thereby maximizing scientific output. The research and development activities performed as part of this project bolstered essential competencies at FRIB in beam physics and ion source technologies, provided valuable training opportunities for junior scientists.
43 PARTICLE ACCELERATORS↗
Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)
The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.
Avni, R.↗