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At least 685 records · Page 38

Revealing ultrafast proton-transfer-mediated autoionization as a source of low-energy electrons in hydrogen-bonded systems

Ionizing radiation can trigger ultrafast proton transfer, a central mechanism in many chemical and biological functions, that in turn can enable or suppress electron relaxation processes and consequently cause abrupt changes in the reaction pathway. This study combines theory and experiment to probe ultrafast relaxation and dissociation in water dimers following inner- and outer-valence photoionization. By tracking electron and nuclear motion simultaneously, we reveal competing fragmentation pathways that produce low-energy electrons, which are key agents in radiation-induced chemistry, including DNA damage. While low-energy electrons are known to arise via intermolecular Coulombic decay, here we identify a faster relaxation mechanism gated by proton transfer following inner-valence ionization, which we call proton-transfer-mediated autoionization. Occurring within 10 femtoseconds, this process alters fragmentation outcomes, yielding either D 3 O + + OD + or D 2 O + + D 2 O + , depending on the interplay of proton migration and hydrogen back-transfer. Our findings underscore the intricate coupling between electronic and nuclear dynamics in hydrogen-bonded systems and establish proton-transfer-mediated autoionization as a significant pathway for low-energy electron generation.

Atomic and molecular interactions with photons↗

Reverse Energy Cascade in Turbulent Weakly Ionized Plasmas

For systems far from equilibrium, the neglect of a role for viscous effects in turbulence may be generally inappropriate when the relaxation time for the molecular process approaches the local flow time (Orou et al. (1996)). Furthermore, for stationary collisional plasmas, the conventional Reynolds number is irrelevant under circumstances where the standard features of turbulence in ordinary gases are observed in the plasma (Johnson et al. (1987)). The current theoretical understanding of these turbulent phenomenon is particularly inadequate for turbulence associated with ionizing shock waves; generally speaking, thermodynamic, acoustic and pressure fluctuations are all seen as amplified across the shock wave followed by a dramatic decay (relaminarization) usually attributed to a lack of importance of viscosity in the turbulent regions. This decay would be accelerated when the flow speed is also reduced due to the importance usually given to the conventional Reynolds number (which is directly proportional to velocity) as a quality of turbulence index. However, evidence supporting this consensus is lacking. By contrast, recent evidence of vanishing triple correlations form De Silva et al. (1996) provides strong support for early theoretical speculation of inherently molecular effects in macroscopic turbulence in Tsuge (1974). This specifically suggests that the role of compressive effects ordinarily associated with the shock wave could be significantly muted by the existence of a strongly turbulent local environment. There is also more recent theoretical speculation (Frisch et al. (1984)) of an inherently and previously unsuspected non-dissipative nature to turbulence, with energy conservation being nurtured by reverse energy cascades in the turbulent fluctuation spectra. Furthermore, the role which might be played by fluctuations on quantum mechanical phenomena and variations in molecular parameters is completely unknown, especially of the sort which might be found in optical spectra. A determination of the role which changing turbulent parameters might play on optical signatures behind a reflected shock wave should therefore provide a useful tool for the evolution of theoretical models for turbulence.

Williams, Kyron↗

New Insights into Secondary Organic Aerosol Formation at the Air–Liquid Interface

Air-liquid interfacial processing of volatile organic compound oxidation has been suggested as an important source of secondary organic aerosols. However, owing to the lack of techniques for in situ air-liquid interface analysis, the detailed interfacial mechanism remains speculative. To obviate this, the analysis of air-liquid interfacial reactions and the dynamics of glyoxal oxidation as a model volatile organic compound using in situ liquid synchrotron-based vacuum ultraviolet single photon ionization mass spectrometry enabled by the system for analysis at the liquid vacuum interface microreactor is reported. This approach allows for determination of reaction intermediates and oxidation products including polymers and oligomers at the air-liquid interface by mass spectral analysis and appearance energy measurements. Furthermore, an expanded reaction mechanism of photooxidation free radical induced reactions as a source of aqueous secondary organic aerosol formation is proposed based on these new results, suggesting that single photon ionization could be applied to provide unique insights into interfacial chemistry changing the earth atmospheric composition.

aqueous secondary organic aerosol, glyoxal, photoo↗

Data Base for CFD Validation

The flow behind the shock wave formed around objects which fly at hypervelocity behaves differently from that of a perfect gas. Molecules become vibrationally excited, dissociated, and ionized. The hot gas may emit or absorb radiation. When the atoms produced by dissociation reach the wall surface, chemical reactions, including recombination, may occur. The thermochemical phenomena of vibration, dissociation, ionization, surface chemical reaction, and radiation are referred to commonly as high-temperature real-gas phenomena. The phenomena cause changes in the dynamic behavior of the flow and the surface pressure and heat transfer distribution around the object. The character of a real gas is described by the internal degrees of freedom and state of constituent molecules; nitrogen and oxygen for air. The internal energy states, rotation, vibration and electronic, of the molecules are excited and, in the limit, the molecular bonds are exceeded and the gas dissociated into atomic and, possibly, ionic constituents. The process of energy transfer causing excitation, dissociation and recombination is a rate process controlled by particle collisions. Binary, two-body, collisions are sufficient to cause internal excitation, dissociation and ionization while three-body collisions are required to recombine the particles into molecular constituents. If the rates of energy transfer are fast with respect to the local fluid dynamic time scale the gas is in, or nearly in, equilibrium. If the energy transfer rates are very slow the gas can be described as frozen. In all other instances, wherein any of the energy exchange rates are comparable to the local fluid time scale, the gas will be thermally or chemically reacting and out of equilibrium. Real gas thermochemical nonequilibrium processes are important in the determination of aerodynamic heating; both convective (including wall catalytic effects) and radiative heating. To illustrate this we consider the hypervelocity flow over a bluff body typical of an atmospheric entry vehicle or an aerospace transfer vehicle (ASTV). The qualitative aspects of a hypersonic flow field over a bluff body are discussed in two parts, forebody and afterbody, with attention to which particular physical effects must be included in an analysis. This will indicate what type of numerical modeling will be adequate in each region of the flow. A bluff forebody flow field is dominated by the presence of the strong bow shock wave and the consequent heating, and chemical reaction of the gas. At high altitude hypersonic flight conditions the thermal excitation and chemical reaction of the gas occur slowly enough that a significant portion of the flow field is in a state of thermochemical nonequilibrium. A second important effect is the presence of the thick boundary layer along the forebody surface. In this region there are large thermal and chemical species gradients due to the interaction of the gas with the wall. Also at high altitudes the shock wave and the boundary layer may become so thick that they merge; in this case the entire shock layer is dominated by viscous effects.

Deiwert, George S.↗

Non-solar UV produced ions observed optically from the 'Crit I' critical velocity ionization experiment

A critical velocity ionization experiment was carried out with a heavily instrumented rocket launched from Wallops Island on May 13, 1986. Two neutral barium beams were created by explosive shaped charges released from the rocket and detonated at 48 deg to B at altitudes near 400 km and below the solar UV cutoff. Critical velocity ionization was expected to form a detectable ion jet along the release field line, but, instead, an ion cloud of fairly uniform intensity was observed stretching from the release field line across to where the neutral barium jet reached sunlight. The process creating these ions must have been present from the time of the release; the efficiency is estimated to be equivalent to an ionization time constant of 1800 sec. This ionization is most likely from collisions between the neutral barium jet and the ambient atmospheric oxygen, and, if so, the cross section for collisional ionization is 9 x 10 to the -18th sq cm.

Stenbaek-Nielsen, H. C.↗

Utilization of the LS-APGD microplasma/orbitrap-FTMS booster system for detection and isotopic analysis of neodymium nanoparticles

Detection and isotopic analysis of particle populations has seen rapid growth across several application areas, including environmental analysis, nuclear forensics, and food safety. The ability to characterize the particles' unique elemental and isotopic fingerprints could provide information related to formation, processing history, and transport. Regarding nuclear forensics, isotopic analysis of particles derived from diverse materials is often used as a tool to trace the origin and processing history. Mass spectrometric-based techniques currently used for particle population analysis often suffer from limited mass resolution, particularly when dealing with real-world samples that are affected by isobaric and polyatomic interferences from the matrix. To address these analytical challenges, we propose a novel method utilizing the liquid sampling-atmospheric pressure glow discharge (LS-APGD) microplasma ionization source coupled to an ultrahigh resolution Orbitrap mass spectrometer, further enhanced with the FTMS X2T Booster data acquisition and processing unit. The FTMS Booster enables acquisition of extended transient times of up to 3 s, significantly improving mass resolution, thereby reducing or even eliminating the need for prior separation of isobaric or polyatomic interferences. Additionally, the detection of low-abundance isotopes was improved by increasing the signal-to-noise (S/N) ratio. As proof of concept, this study demonstrates the feasibility of the LS-APGD/Orbitrap-FTMS X2T Booster platform for direct analysis using a suspension of well-characterized ∼120 nm neodymium particles. The quality of the isotope ratios values obtained from a few hundred particles were in good agreement with those obtained from homogeneous ionic solutions. These results highlight the potential of the LS-APGD/Orbitrap platform for rapid, accurate, and interference-resilient isotope ratio analysis of particle populations without the need for dissolution and subsequent chemical separations, offering significant advantages for nuclear forensics, safeguards, and environmental applications. The effort here also points to further paths forward, hopefully towards single particle (SP) analysis using microplasma ionization and the ultrahigh resolving power of the Orbitrap mass analyzer.

FTMS X2T booster↗

Multi-fluid and kinetic models of partially ionized magnetic reconnection

Magnetic reconnection in partially ionized plasmas is a ubiquitous and important phenomenon in both laboratory and astrophysical systems. Here, simulations of partially ionized magnetic reconnection with well-matched initial conditions are performed using both multi-fluid and fully-kinetic approaches. Despite similar initial conditions, the time-dependent evolution differs between the two models. In multi-fluid models, the reconnection rate locally obeys either a decoupled Sweet–Parker scaling, where neutrals are unimportant, or a fully coupled Sweet–Parker scaling, where neutrals and ions are strongly coupled, depending on the resistivity. In contrast, kinetic models show a faster reconnection rate that is proportional to the fully-coupled, bulk Alfvén speed, $v^*_A$. In this work, these differences are interpreted as the result of operating in different collisional regimes. Multi-fluid simulations are found to maintain $ν_{ni}L/v^*_A$ ≳1, where $ν_{ni}$ is the neutral–ion collision frequency and L is the time-dependent current sheet half-length. This strongly couples neutrals to the reconnection outflow, while kinetic simulations evolve to allow $ν_{ni}L/v^*_A$ <1, decoupling neutrals from the reconnection outflow. Differences in the way reconnection is triggered may explain these discrepancies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Effect of ionizing radiation on PuO2 and surrogate oxide materials under storage conditions

The stockpile of plutonium separated from used nuclear fuel amounts to many 100s of tonnes. The majority of this plutonium is stored as PuO2 powder packaged in multi-can containers. The conditions during the packaging of reprocessed PuO2 for long term storage are closely controlled to limit water uptake as radiolytic decomposition of any adsorbed water will lead to the formation of both a potentially flammable atmosphere containing molecular hydrogen as well as reactive oxygen species which may be incorporated into the oxide phase. Consequently, the safety case for the long-term storage of PuO2 requires a complete understanding of the fundamental physical, chemical and materials degradation processes occurring at the water-oxide interface inside the storage canisters. This study investigates the effect of ionizing radiation on PuO2 and various surrogate oxides under atmospheres potentially encountered in storage canisters.

11 - NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Ionizing Organic Compound Based Nanocomposites for Efficient Gamma-Ray Sensor

Thin film and nanocrystalline materials of oxides have been very attractive choice as low cost option for gamma-ray detection and have shown great promise. Our studies on pure oxide films indicated that thickness and microstructure have pronounced effect on sensitivity. Since the interaction of gamma-ray with composites involves all three interaction processes; photoelectric effect, Compton scattering, and pair production, composites containing ionic organics have better chance for enhancing sensitivity. In the composites of ionizing organics oxidation effect of unusual oxides changes much faster and hence increases the sensitivity of radiation. In this study, we have used nickel oxide and titanium oxide in ionic organics to develop composite materials for low energy gamma-ray sensing. We prepared composites containing ethylene carbonate and evaluated the effect of commercial Cs-137 radiation source by studying current-voltage relationship at several frequencies. Radiated samples showed higher resistivity compared to as prepared composites.

Singh, N. B.↗

Angle-resolved nonresonant two-photon single ionization of argon using 9.3-eV photons produced via high-order harmonic generation

Here we present an experimental study on the photoionization dynamics of nonresonant one-color two-photon single valence ionization of neutral argon atoms. Using 9.3-eV photons produced via high harmonic generation and a three-dimensional momentum imaging spectrometer, we detect the photoelectrons and ions produced from nonresonant two-photon ionization in coincidence. Photoionization from the $3p$ orbital produces a photoelectron scattering wave function with $p$- and $f$-partial-wave components, which interfere and result in a photoelectron angular distribution with peak amplitude perpendicular to the vacuum ultraviolet polarization. The comparison between the present results and the two previous sets of theoretical calculations [Phys. Rev. A 44, 324 (1991), and J. Phys. B: At. Mol. Phys. 16, 2737 (1983)] indicates that electron-electron correlation contributes appreciably to the two-photon ionization dynamics.

74 ATOMIC AND MOLECULAR PHYSICS↗

Parametric optimization of the liquid sampling-atmospheric pressure glow discharge ionization source coupled to an Orbitrap mass spectrometer for neodymium isotope ratio determinations

Isotope ratio determinations are a valuable tool in several application areas. In nuclear forensics, the isotope ratios of uranium and plutonium are commonly used as a signature for the nuclear material's provenance and processing history. However, signatures from other coexisting elements, such as neodymium and samarium, can offer additional insights. Here, the liquid sampling-atmospheric pressure glow discharge (LS-APGD) ionization source coupled to an Orbitrap mass spectrometer (MS) has demonstrated its utility for actinide measurements. This instrumental platform can leverage the high resolution offered by the Orbitrap MS to overcome potential isobaric interferences, such as 144 Nd- 144 Sm, 148 Nd- 148 Sm, and 150 Nd- 150 Sm pairs. The work presented herein demonstrates the rapid, accurate, and precise determination of the isotope ratios for neodymium using the LS-APGD/Orbitrap MS. Both the LS-APGD and Orbitrap MS parameters were optimized systematically, with NdO + found to be the most abundant, most reduced species after applying the optimal collision-induced dissociation modalities. A limit of detection of 3 pg of 142 Nd was achieved when data was acquired and processed using the FTMS Booster, an external data acquisition and processing system offered by Spectroswiss. Excellent accuracy of better than 99 % and precision of <1 % RSD were achieved when a solution of the well-characterized neodymium standard (JNdi-1 standard) was analyzed under the optimized condition, indicating the LS-APGD/Orbitrap's great potential for isotope ratio analysis of Nd and other REEs for diverse applications.

47 OTHER INSTRUMENTATION↗

Rocket observations of solar UV radiation during the eclipse of 7 March 1970.

Results of observations of the solar eclipse of Mar. 7, 1970, with photometers sensitive to narrow bands of radiation at Lyman-alpha (1216 A) and at 2600 A included in the payloads of four Nike Apache rockets flown before and during the eclipse. At the center of totality, the flux of Lyman-alpha from the solar corona is 0.15% of the flux from the unobscured sun. The flux at second contact is 0.64%; at third contact, two observations give 0.52 and 0.59%. The brightness of the chromosphere in Lyman-alpha decreases exponentially over the range from 5 to 30 arc-sec from the limb with a scale height of 3835 plus or minus 70 km. In addition to the coronal and chromospheric Lyman-alpha a diffuse source is found. This is restricted to within 20 deg of the earth's horizon and is nearly uniform in azimuth at 170 km, the flux is about 3% of that from the unobscured sun. The flux of Lyman-alpha during the eclipse is considered in relation to the observed variation in electron density. It is concluded that, in totality, the ionosphere near 80 km is not in equilibrium with the ionizing radiation and that the production rate for electrons is not negligible if the loss process is recombination; it is negligible if the loss process is attachment-like.

Smith, L. G.↗

On ionization in H I regions

A comparison is made of the K I, Na I, Ca II, and H I interstellar absorption lines formed in relatively low-density interstellar clouds in H I regions. The data indicate that the fractional ionization (ratio of electron density to hydrogen density) is nearly constant for a range in hydrogen densities covering a factor of 15. If ionization balance exists in the clouds, then ionization of hydrogen by either low-energy cosmic rays or soft X-rays cannot be the principal source of the observed free electrons, and the hydrogen ionization rate is less than 10 to the -16th power per sec for these processes.

Hobbs, L. M.↗

Chemistry of the thermosphere and ionosphere

In the present paper, some of the most important features of the Atmosphere Explorer program, involving studies of the chemistry of the ionosphere and thermosphere, are reviewed. Solar flux and cross sections are tabulated, along with the revised reference spectrum F47113 as compared with the preliminary R74113. The principal results examined include some unexpected variations in the EUV flux and in the response of the thermosphere, revealed by extreme ultraviolet spectrophotometers; discrepancies between the measured and calculated electron flux; recent developments in the detection of nocturnal mid- and low-latitude sources of ionization; and the application of AE satellite data to the study of ionospheric and thermospheric processes, rate coefficients, and atomic and molecular processes.

Torr, D. G.↗

SMM observations of K-alpha radiation from fluorescence of photospheric iron by solar flare X-rays

High-resolution Fe K-alpha spectra near 1.94 A observed during solar flares with the Bent Crystal Spectrometer on the Solar Maximum Mission are presented. The evidence for two possible excitation mechanisms, electron impact and fluorescence, is examined. It is found that the fluorescence mechanism satisfactorily describes the results, while the observations do not support electron collisional excitation of the Fe K-alpha transitions in low ionization stages (II-XII) of iron. Using Bai's model of the fluorescent excitation process, the photospheric iron abundance relative to that of hydrogen is estimated to be 5-6 x 10 to the -5th. The mean height of the soft X-ray source producing the K-alpha fluorescence is calculated on the basis of this model for about 40 large flares. The solar K-alpha lines are found to be about 25 percent wider than those measured in the laboratory. Weak line features observed at wavelengths shorter than that of the K-alpha lines are discussed.

Parmar, A. N.↗

Theoretical survey on positronium formation and ionisation in positron atom scattering

The recent theoretical studies are surveyed and reported on the formation of exotic atoms in positron-hydrogen, positron-helium and positron-lithium scattering specially at intermediate energy region. The ionizations of these targets by positron impact was also considered. Theoretical predictions for both the processes are compared with existing measured values.

Basu, Madhumita↗

PAHs molecules and heating of the interstellar gas

Until now it has remained difficult to account for the rather high temperatures seen in many diffuse interstellar clouds. Various heating mechanisms have been considered: photoionization of minor species, ionization of H by cosmic rays, and photoelectric effect on small grains. Yet all these processes are either too weak or efficient under too restricting conditions to balance the observed cooling rates. A major heat source is thus still missing in the thermal balance of the diffuse gas. Using photoionization cross sections measured in the lab, it was shown that in order to balance the observed cooling rates in cold diffuse clouds (T approx. 80 K) the PAHs would have to contain 15 percent of the cosmic abundance of carbon. This value does not contradict the former estimation of 6 percent deduced from the IR emission bands since this latter is to be taken as a lower limit. Further, it was estimated that the contribution to the heating rate due to PAH's in a warm HI cloud, assuming the same PAH abundance as for a cold HI cloud, would represent a significant fraction of the value required to keep the medium in thermal balance. Thus, photoionization of PAHs might well be a major heat source for the cold and warm HI media.

Verstraete, Laurent↗

Elemental and charge state composition of the fast solar wind observed with SMS instruments on WIND

The elemental composition and charge state distributions of heavy ions of the solar wind provide essential information about: (1) atom-ion separation processes in the solar atmosphere leading to the 'FIP effect' (the overabundance of low First Ionization potential (FIP) elements in the solar wind compared to the photosphere); and (2) coronal temperature profiles, as well as mechanisms which heat the corona and accelerate the solar wind. This information is required for solar wind acceleration models. The SWICS instrument on Ulysses measures for all solar wind flow conditions the relative abundance of about 8 elements and 20 charge states of the solar wind. Furthermore, the Ulysses high-latitude orbit provides an unprecedented look at the solar wind from the polar coronal holes near solar minimum conditions. The MASS instrument on the WIND spacecraft is a high-mass resolution solar wind ion mass spectrometer that will provide routinely not only the abundances and charge state of all elements easily measured with SWICS, but also of N, Mg, S. The MASS sensor was fully operational at the end of 1994 and has sampled the in-ecliptic solar wind composition in both the slow and the corotating fast streams. This unique combination of SWICS on Ulysses and MASS on WIND allows us to view for the first time the solar wind from two regions of the large coronal hole. Observations with SWICS in the coronal hole wind: (1) indicate that the FIP effect is small; and (2) allow us determine the altitude of the maximum in the electron temperature profile, and indicate a maximum temperature of approximately 1.5 MK. New results from the SMS instruments on Wind will be compared with results from SWICS on Ulysses.

Gloeckler, G.↗