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At least 181 records · Page 10

Ultrafast dynamics of CN radical reactions with chloroform solvent under vibrational strong coupling

Polariton chemistry may provide a new means to control molecular reactivity, permitting remote, reversible modification of reaction energetics, kinetics, and product yields. A considerable body of experimental and theoretical work has already demonstrated that strong coupling between a molecular vibrational mode and the confined electromagnetic field of an optical cavity can alter chemical reactivity without external illumination. However, the mechanisms underlying cavity-altered chemistry remain unclear in large part because the experimental systems examined previously are too complex for detailed analysis of their reaction dynamics. Here, we experimentally investigate photolysis-induced reactions of cyanide radicals with strongly-coupled chloroform (CHCl 3 ) solvent molecules and examine the intracavity rates of photofragment recombination, solvent complexation, and hydrogen abstraction. Here we use a microfluidic optical cavity fitted with dichroic mirrors to facilitate vibrational strong coupling (VSC) of the C–H stretching mode of CHCl 3 while simultaneously permitting optical access at visible wavelengths. Ultrafast transient absorption experiments performed with cavities tuned on- and off-resonance reveal that VSC of the CHCl 3 C–H stretching transition does not significantly modify any measured rate constants, including those associated with the hydrogen abstraction reaction. This work represents, to the best of our knowledge, the first experimental study of an elementary bimolecular reaction under VSC. We discuss how the conspicuous absence of cavity-altered effects in this system may provide insights into the mechanisms of modified ground state reactivity under VSC and help bridge the divide between experimental results and theoretical predictions in vibrational polariton chemistry.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Connecting collisional and photofragmentation resonances in the ungerade symmetry states of H 2

A recently developed energy-dependent frame transformation theory that incorporates both ionisation and dissociation channels of the H 2 molecule, is extended to treat the ungerade states that occur both in dissociative recombination and as the final state in ground state photoabsorption. The theoretical treatment includes the rotational degrees of freedom and is benchmarked against a two-dimensional model that can be solved with high accuracy and also compared with photoabsorption experiments. Analysis of the resulting spectra demonstrates how the same resonances appear in very different observables, often with quite different line shapes.

74 ATOMIC AND MOLECULAR PHYSICS↗

CHEQUP v0.1

CHEQUP (Castro-based Hofi Expansion with QUasineutral Plasma) is a simulation code for modeling the formation of hydrodynamic optical-field-ionized (HOFI) plasma channels, which are used as waveguides in laser-plasma acceleration experiments. This includes experiments performed at LBNL's BELLA facility as well as other laser facilities across the world. CHEQUP extends the open-source Castro hydrodynamics framework with physics modules tailored for modeling HOFI plasma channels -- including multi-species ionization and three-body recombination for mixtures of hydrogen, nitrogen, helium, and argon ; a two-temperature model tracking electron and heavy-species temperatures separately ; and coupling with other codes of the BLAST ecosystem (https://blast.lbl.gov/) such as WarpX, via the openPMD standard. CHEQUP inherits from Castro the ability to run on modern GPU architectures (NVIDIA CUDA, AMD HIP) and supports adaptive mesh refinement (AMR) for efficient multi-scale resolution. Compared to existing tools, CHEQUP would be, to our knowledge, the first open-source code implementing the full HOFI channel formation physics, and the first implementation capable of running on GPUs. This enables significantly faster, large-scale parameter scans critical for the design of next-generation LPA-based accelerators and light sources.

Lehe, Remi [Lawrence Berkeley National Laboratory ↗

Fast molecular shocks. II - Emission from fast dissociative shocks

The line radiations emitted in the cooling gas behind a fast dissociative shock are studied. The intensities emitted in high rotational transitions of the neutral molecules CO, SiO, HCN, CN, NO, and SO are estimated, as well as in rovibrational transitions of the molecular ions HeH(+) and OH(+) in radio recombination lines of atomic hydrogen and in fine-structure transitions of C, C(+), O, and Si(+). The predictions are compared with the observed intensities of line emission from the Orion-KL region. For Orion-KL the observations do not exclude, but probably do not require, the presence of a fast dissociative shock. Emission from SiO in high-J rotational states and from vibrationally excited OH(+), HeH(+), HeH(+), and SO(+) may be detectable from dissociative shocks under suitable conditions of preshock density and shock velocity; such emission may prove to be a useful diagnostic probe of fast shock activity.

Neufeld, David A.↗

An infrared jet in Centaurus A (NGC 5128): Evidence for interaction between the active nucleus and the interstellar medium

In the present study, higher resolution near infrared images of the visually-obscured central region of Centaurus A were obtained in order to investigate the effects of the active nucleus on the surrounding galaxy. Researchers present J(1.25 microns), H(1.65 microns), and K(2.2 microns) images of the central 40 seconds of the galaxy, taken with the Univ. of Texas InSb array camera on the Anglo Australian 3.9 meter telescope. These images reveal a jet extending approx. 10 arcseconds to the northeast of the nucleus at the same position angle as the x ray and radio jets. The infrared jet is most prominent at the shortest wavelength (1.25 microns), where its brightness surpasses that of the nucleus. The blue appearance of the infrared jet is remarkable considering the heavy obscuration that is evident at visual wavelengths. The amount of reddening in the vicinity of the jet is determined from the measured colors of the stellar core of the galaxy, and this value is used to generate an extinction-corrected energy distribution. In contrast to previously studied optical and infrared jets in active nuclei, the short-wavelength prominence of the Cen A jet indicates that it cannot be attributed to synchrotron emission from a beam of relativistic electrons. The remaining viable mechanisms involve an interaction between the interstellar medium and the active nucleus: the infrared radiation from the jet may be due to emission from interstellar gas that has been entrained and heated by the flow of relativistic particles from the nucleus; alternatively, luminous blue stars may have been created by compression of interstellar material by the relativistic plasma. To investigate these proposed mechanisms, near-infrared spectroscopic studies of Cen A are in progress to look for collisionally excited molecular hydrogen emission lines and recombination lines from ionized gas.

Joy, Marshall↗

Replication of the Apparent Excess Heat Effect in a Light Water-Potassium Carbonate-Nickel Electrolytic Cell

Replication of experiments claiming to demonstrate excess heat production in light water-Ni-K2CO3 electrolytic cells was found to produce an apparent excess heat of 11 W maximum, for 60 W electrical power into the cell. Power gains range from 1.06 to 1.68. The cell was operated at four different dc current levels plus one pulsed current run at 1 Hz, 10% duty cycle. The 28 liter cell used in these verification tests was on loan from a private corporation whose own tests with similar cells are documented to produce 50 W steady excess heat for a continuous period exceeding hundreds of days. The apparent excess heat can not be readily explained either in terms of nonlinearity of the cell's thermal conductance at a low temperature differential or by thermoelectric heat pumping. However, the present data do admit efficient recombination of dissolved hydrogen-oxygen as an ordinary explanation. Calorimetry methods and heat balance calculations for the verification tests are described. Considering the large magnitude of benefit if this effect is found to be a genuine new energy source, a more thorough investigation of evolved heat in the nickel-hydrogen system in both electrolytic and gaseous loading cells remains warranted.

Niedra, Janis M.↗

A Comparison of Ultraviolet, Optical, and X-Ray Imagery of Selected Fields in the Cygnus Loop

During the Astro-1 and Astro-2 Space Shuttle missions in 1090 and 199.5, far ultraviolet (FUV) images of five 40' diameter fields around the rim of the Cygnus Loop supernova remnant were observed with the Ultraviolet Imaging Telescope (UIT). These fields sampled a broad range of conditions including both radiative and nonradiative shocks in various geometries and physical scales. In these shocks, the UIT B5 band samples predominantly C IV Lambda-1550 and the hydrogen two-photon recombination continuum. Smaller contributions are made by emission lines of He II Lambda-1640 and O III] Lambda-1665. We present these new FUV images and compare them with optical H-alpha and [O III], and ROSAT HRI X-ray images. Comparing the UIT images with those from the other bands provides new insights into the spatial variations and locations of these different types of emission. By comparing against shock model calculations and published FUV spectroscopy at select locations, we surmise that resonance scattering in the strong FUV permitted lines is widespread in the Cygnus Loop. especially in the bright optical filaments typically selected for observation in most previous studies.

Danforth, Charles W.↗

New Propellants and Cryofuels

The proposed research will investigate the stability and cryogenic properties of solid propellants that are critical to NASA s goal of realizing practical propellant designs for future spacecraft. We will determine the stability and thermal properties of a solid hydrogen-liquid helium stabilizer in a laboratory environment in order to design a practical propellant. In particular, we will explore methods of embedding atomic species and metallic nano-particulates in hydrogen matrices suspended in liquid helium. We will also measure the characteristic lifetimes and diffusion of atomic species in these candidate cryofuels. The most promising large-scale advance in rocket propulsion is the use of atomic propellants; most notably atomic hydrogen stabilized in cryogenic environments, and metallized-gelled liquid hydrogen (MGH) or densified gelled hydrogen (DGH). The new propellants offer very significant improvements over classic liquid oxygen/hydrogen fuels because of two factors: (1) the high energy-release, and (ii) the density increase per unit energy release. These two changes can lead to significant reduced mission costs and increased payload to orbit weight ratios. An achievable 5 to 10 percent improvement in specific impulse for the atomic propellants or MGH fuels can result in a doubling or tripling of system payloads. The high-energy atomic propellants must be stored in a stabilizing medium such as solid hydrogen to inhibit or delay their recombination into molecules. The goal of the proposed research is to determine the stability and thermal properties of the solid hydrogen-liquid helium stabilizer. Magnetic resonance techniques will be used to measure the thermal lifetimes and the diffusive motions of atomic species stored in solid hydrogen grains. The properties of metallic nano-particulates embedded in hydrogen matrices will also be studied and analyzed. Dynamic polarization techniques will be developed to enhance signal/noise ratios in order to be able to detect low concentrations of the introduced species. The required lifetimes for atomic hydrogen and other species can only be realized at low temperatures to avoid recombination of atoms before use as a fuel.

Palasezski, Bryan↗

Process Research of Polycrystalline Silicon Material (PROPSM)

An investigation was begun into the usefulness of molecular hydrogen annealing on polycrystalline solar cells. No improvement was realized even after twenty hours of hydrogenation. Thus, samples were chosen on the basis of: (1) low open circuit voltage; (2) low shunt conductance; and (3) high light generated current. These cells were hydrogenated in molecular hydrogen at 300 C. The differences between the before and after hydrogenation values are so slight as to be negligible. These cells have light generated current densities that indicate long minority carrier diffusion lengths. The open circuit voltage appears to be degraded, and quasi-neutral recombination current enhanced. Therefore, molecular hydrogen is not usful for passivating electrically active defects.

Culik, J. S.↗

Atomic hydrogen as a launch vehicle propellant

An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb (sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 1b(sub f)/s/lb(sub m) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

Palaszewski, Bryan A.↗

Atomic hydrogen as a launch vehicle propellant

An analysis of several atomic hydrogen launch vehicles was conducted. A discussion of the facilities and the technologies that would be needed for these vehicles is also presented. The Gross Liftoff Weights (GLOW) for two systems were estimated; their specific impulses (I sub sp) were 750 and 1500 lb(sub f)/s/lb(sub m). The atomic hydrogen launch vehicles were also compared to the currently planned Advanced Launch System design concepts. Very significant GLOW reductions of 52 to 58 percent are possible over the Advanced Launch System designs. Applying atomic hydrogen propellants to upper stages was also considered. Very high I(sub sp) (greater than 750 lb(sub f)/s/lb(sub m)) is needed to enable a mass savings over advanced oxygen/hydrogen propulsion. Associated with the potential benefits of high I(sub sp) atomic hydrogen are several challenging problems. Very high magnetic fields are required to maintain the atomic hydrogen in a solid hydrogen matrix. The magnetic field strength was estimated to be 30 kilogauss (3 Tesla). Also the storage temperature of the propellant is 4 K. This very low temperature will require a large refrigeration facility for the launch vehicle. The design considerations for a very high recombination rate for the propellant are also discussed. A recombination rate of 210 cm/s is predicted for atomic hydrogen. This high recombination rate can produce very high acceleration for the launch vehicle. Unique insulation or segmentation to inhibit the propellant may be needed to reduce its recombination rate.

Palaszewski, Bryan A.↗

Collisional Ionization Equilibrium for Optically Thin Plasmas

Reliably interpreting spectra from electron-ionized cosmic plasmas requires accurate ionization balance calculations for the plasma in question. However, much of the atomic data needed for these calculations have not been generated using modern theoretical methods and their reliability are often highly suspect. We have utilized state-of-the-art calculations of dielectronic recombination (DR) rate coefficients for the hydrogenic through Na-like ions of all elements from He to Zn. We have also utilized state-of-the-art radiative recombination (RR) rate coefficient calculations for the bare through Na-like ions of all elements from H to Zn. Using our data and the recommended electron impact ionization data of Mazzotta et al. (1998), we have calculated improved collisional ionization equilibrium calculations. We compare our calculated fractional ionic abundances using these data with those presented by Mazzotta et al. (1998) for all elements from H to Ni, and with the fractional abundances derived from the modern DR and RR calculations of Gu (2003a,b, 2004) for Mg, Si, S, Ar, Ca, Fe, and Ni.

Bryans, P.↗

Implications of high-pressure oxygen hydrates on radiolytic oxygen in Jovian icy moons

Various icy moons, such as Europa and Ganymede, have thin oxygen atmospheres and exhibit spectral features attributed to oxygen held in their surface ices. The oxygen forms from the radiolysis of water. The interiors of these bodies are subject to high pressures and it is not known how deep into icy moons oxygen-bearing ices can penetrate, or the structures formed by the oxygen–water system at high pressure. Here, we show that oxygen hydrates are stable to 2.6 GPa, allowing them to penetrate deep into icy moons, both above and below proposed sub-surface liquid-water oceans. Similarities between oxygen and hydrogen hydrates indicate potentially enhanced recombination rates, transforming them back into water and offering a resolution to the discrepancy between predicted and measured radiolysis rates. In addition to the low-pressure CS-II clathrate, our results find three high-pressure phases in the oxygen–water system: an ST clathrate, a C 0 hydrate, and a filled ice isomorphous with methane hydrate III. This shows a vast storage potential for molecular oxygen in icy moons and indicates that Europa could still be absorbing oxygen into its crustal ice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Variation with Temperature of the Recombination of Oxygen Atoms on a Platinum Surface

The development of vehicles capable of flight at high Mach speeds and at extreme altitudes has re-stimulated interest in the "catalytic efficiency" of metals for recombination of atomic species of hydrogen, oxygen, and nitrogen. Most of the work to date has been of an exploratory nature, comparing the relative efficiencies of the different metals.

Fryburg, George C.↗

Limits on the extent of Saturn's hydrogen cloud

The 30-day reports from the Voyager Ultraviolet Spectrometer team characterize the atomic hydrogen observed near Saturn as a torus with a half width of 7 Saturnian radii. The atomic processes occurring in the inner magnetosphere are modelled, including sputtering, ionization, charge exchange, ion-atom interchange, recombination, and transport, and a neutral hydrogen source is added to test the proposal that a hydrogen cloud exists in this region. Plasma observations in the inner magnetosphere are found to be inconsistent with the presence of a dense atomic hydrogen cloud. Thus, it is concluded that the hydrogen cloud must be a torus as originally reported, and that the cloud does not extend inward to the orbits of the inner satellites of Saturn.

Richardson, John D.↗

The characteristics of sealed nickel-cadmium cells during voltage reversal

A mechanism which allows a cell voltage reversal in a nickel cadmium battery are discussed. The effects of reconditioning and the characteristics of Ni-Cd cells during voltage reversal at low overdischarge rates are outlined. Graphs are presented for: (1) hydrogen pressure decay-effect of state of charge (open circuit stand); (2) hydrogen pressure increase during overdischarge; (3) hydrogen pressure decay-effect of temperature (cells terminals connected through resistors); (4) cell, positive and negative electrode voltage during reversal when reconditioning a 13 cell-24-Ah battery pack through a 40 Omega resistor; (5) pressure discharge current and recombination current during voltage reversal when reconditioning a 13 cell-24-Ah battery pack through a 40 Omega resistor; (6) theoretical hydrogen gas pressure if there were no recombination; and (7) effect of hydrogen pressure on recombination rate during overcharge.

Ritterman, P. F.↗