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At least 523 records · Page 29

Minimum Energy Pathways for Chemical Reactions

Computed potential energy surfaces are often required for computation of such parameters as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method to obtain accurate energetics, gives useful results for a number of chemically important systems. The talk will focus on a number of applications to reactions leading to NOx and soot formation in hydrocarbon combustion.

Walch, S. P.↗

Exploring the Continuum of Stratiform and Cumulus Cloudiness: Observational Insights Related to Marine Boundary Layer Clouds

Low-level marine clouds take on a wide range of morphological states owing to external forcing and internal feedbacks. Rarely are shallow marine clouds adequately described by a single simplified framework but instead exhibit features that partially conform to several states that could be considered “limiting”. Perhaps the most apparent dichotomy is whether to consider shallow clouds as existing within a surface-driven mixed layer or as convective “plume” elements positioned on top. Do the rules that govern the limiting cases transition smoothly through the hybrid scenarios found in nature, or are there particular regions of attraction or repulsion?We have identified 3 ”axes” along which to investigate how the energetics, thermodynamics and cloud macro structure relate to the intermediate spaces between idealizations.

Ewan Crosbie↗

Thermomechanical phenomena in high speed rubbing

An analytical approach is presented for the modeling of the thermomechanical interactions which occur in high speed sliding situations. These sliding contact problems which are characterized by active and interrelated thermal and mechanical phenomena could be called 'rub energetics' problems. Analytical models were developed to simulate two different rub situations: high energy braking of disk brakes and high speed rubs of gas path seals in turbine engines. The models proved to be particularly useful in predicting the severe temperatures and deformations near hot contact patches on the rubbing surfaces. The size of the hot patches is generally determined by normal load and the properties of the contacting materials. Temperatures at the contact patches can approach the melting point of the materials, especially at high sliding velocities. These high temperatures can lead to large amounts of near-surface deformation and high wear rates. Decreased contact temperatures can result from using materials with increased thermal conductivity and increased heat capacity or choosing mechanical properties (decreased stiffness, yield stress or coefficient of thermal expansion) which give larger hot spot size.

Kennedy, F. E.↗

Calibration and performance of the energetic X-ray imaging telescope experiment

The final integration and testing of the Energetic X-ray Imaging Telescope Experiment (EXITE) are described. The detector and telescope as finally assembled are described, and problems as well as solutions are detailed. The preflight calibration of the position-sensitive NaI detector revealed unanticipated effects in the energy spectra. In particular, an effect due to surface roughness (lack of firm optical polishing) on the crystal was found and calibrated. The radial variation of gain and resolution in the detector was also measured, and so-called flat fielding methods have been derived to analyze the data. The integration of the EXITE detector and gondola systems is described. Several novel features were developed for the EXITE gondola, most notably a shock absorber system. The performance of the detector and gondola systems was evaluated on a first balloon flight from Australia (May 1988) and a second flight from Ft. Sumner, New Mexico (October 1988).

Braga, Joao↗

Computational and Experimental Study of Energetic Materials in a Counterflow Microgravity Environment

Counterflow diffusion flames are studied for various fuels flowing against decomposition products from solid ammonium perchlorate (AP) pellets in order to obtain fundamental understanding of composite propellant flame structure and chemistry. We illustrate this approach through a combined experimental and numerical study of a fuel mixture consisting of C2H4 CO + H2, and C2H2 + C2H4 flowing against solid AP. For these particular AP-fuel systems, the resulting flame zone simulates the various flame structures that are ex+ to exist between reaction products from Ap crystals and a hydrocarbon binder. As in all our experimental studies, quantitative species and temperature profiles have been measured between the fuel exit and AP surface. Species measured included CN, NH, NO, OH, N2, CO2, CO, H2, CO, HCl, and H2O. Temperature was measured using a thermocouple at the exit, spontaneous Raman scattering measurements throughout the flame, OH rotational population distributions, and NO vibrational population distributions. The burning rate of AP was also measured as a function of strain rate, given by the separation distance between the AP surface and the gaseous hydrocarbon fuel tube exit plane. This distance was nominally set at 5 mm, although studies have been performed for variations in separation distance. The measured 12 scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 86 species and 531 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particle size distributions are varied. Furthermore, the results constitute the continued development of a necessary database and validation of a comprehensive model for studying more complex AP-solid fuel systems in microgravity. Exploratory studies have also been performed with liquid and solid fuels at normal gravity. Because of melting (and hence dripping) and deep thermal wave penetration into the liquid, these experiments were found feasible, but not used for obtaining quantitative data. Microgravity experiments are needed to eliminate the dripping and boiling phenomena of these systems at normal gravity. Microgravity tests in the NASA Glenn 2.2 second drop tower were performed (1) to demonstrate the feasibility of performing propellant experiments using the NASA Glenn microgravity facilities, (2) to develop the operational procedures for safe handing of the energetic materials and disposal of their toxic combustion by-products and (3) to obtain initial measurements of the AP burning rate and flame structure under microgravity conditions. Experiments were conducted on the CH4/AP system previously studied at normal gravity using a modified design of the counterflow burner and a NASA Glenn Pig Rig, i.e., one of the existing drop rigs for general-purpose usage. In these experiments, the AP burning rate was measured directly with a linear variable differential transducer (LVDT) and video imaging of the flame structure was recorded ignition was achieved by hot wires stretched across the AP surfaces. Initial drop tower combustion data show that with the same burner separation distance and flow conditions of the normal gravity experiments, the AP burning rate is approximately a factor of two lower. This difference is likely a result of radiation effects, but further tests with longer test times need to be conducted to verify that steady state conditions were achieved under microgravity conditions.

Takahashi, Fumiaki↗

Radio emission from Io

Radio observations of Io taken with the VLA at 2, 6, and 21 cm show flux densities of 11.6 + or - 0.2 mJy, and less than 0.5 mJy, respectively, where the latter is a 2 sigma upper limit. These flux densities correspond to Io disk brightness temperatures of T(b) (2 cm) = 98 + or - 17 K, T(b) (6 cm) = 85 + or - 16 K, and T(b) (21 cm) less than 400 K, respectively. These radio brightness temperatures are consistent with thermal emission expected from Io's surface on the basis of its infrared brightness temperature and its radio emissivity derived from radar studies. No evidence for nonthermal radio emission from Io is found, such as has been reported by Mingaliev et al (1979). By using a model for the generation of synchrotron emission at 21 cm by energetic electrons in a hypothetical Io magnetosphere, an upper limit of Io's dipole magnetic moment less than 2 x 10 to the 25th gauss/cu cm is found.

De Pater, I.↗

Magnetospheric mapping with quantitative geomagnetic field models

The Mead-Fairfield geomagnetic field models were used to trace field lines between the outer magnetosphere and the earth's surface. The results are presented in terms of ground latitude and local time contours projected to the equatorial plane and into the geomagnetic tail. With these contours various observations can be mapped along field lines between high and low altitudes. Low altitudes observations of the polar cap boundary, the polar cusp, the energetic electron trapping boundary and the sunward convection region are projected to the equatorial plane and compared with the results of the model and with each other. The results provide quantitative support to the earlier suggestions that the trapping boundary is associated with the last closed field line in the sunward hemisphere, the polar cusp is associated with the region of the last closed field line, and the polar cap projects to the geomagnetic tail and has a low latitude boundary corresponding to the last closed field line.

Fairfield, D. H.↗

Gamma rays from grazing incidence cosmic rays in the earth's atmosphere

Interactions of grazing incidence, ultra high-energy cosmic rays with the earth's atmosphere may provide a new method of studying energetic cosmic rays with gamma-ray satellites. It is found that these cosmic ray interactions may produce gamma-rays on millisecond timescales which may be detectable by satellites. An extremely low gamma-ray background for transient gamma-ray events and a large area of interaction, the earth's surface, make the scheme plausible. The effective cross section of detection of interactions for cosmic rays above 10(exp 20) eV is found to be more than two orders of magnitude higher than Earth-based detection techniques. This method may eventually offer an efficient way of probing this region of the cosmic-ray energy spectrum where events are scarce. In this paper, a conceptual model is presented for the production of short bursts of gamma-rays based on these grazing incidence encounters with the Earth's atmosphere.

Ulmer, Andrew↗

Pair Production and Gamma-Ray Emission in the Outer Magnetospheres of Rapidly Spinning Young Pulsars

Electron-positron pair production and acceleration in the outer magnetosphere may be crucial for a young rapidly spinning canonical pulsar to be a strong Gamma-ray emitter. Collision between curvature radiated GeV photons and soft X-ray photons seems to be the only efficient pair production mechanism. For Crib-like pulsars, the magnetic field near the light cylinder is so strong, such that the synchrotron radiation of secondary pairs will be in the needed X-ray range. However, for majority of the known Gamma-ray pulsars, surface emitted X-rays seem to work as the matches and fuels for a gamma-ray generation fireball in the outer magnetosphere. The needed X-rays could come from thermal emission of a cooling neutron star or could be the heat generated by bombardment of the polar cap by energetic particles generated in the outer magnetosphere. With detection of more Gamma-ray pulsars, it is becoming evident that the neutron star's intrisic geometry (the inclination angle between the rotation and magnetic axes) and observational geometry (the viewing angle with respect to the rotation axis) are crucial to the understanding of varieties of observational properties exhibited by these pulsars. Inclination angles for many known high energy Gamma-ray pulsars appear to be large and the distribution seems to be consistent with random orientation. However, all of them except Geminga are pre-selected from known radio pulsars. The viewing angles are thus limited to be around the respective inclination angles for beamed radio emission, which may induce strong selection effect. The viewing angles as well as the inclination angles of PSR 1509-58 and PSB 0656+14 may be small such that most of the high energy Gamma-rays produced in the outer accelerators may not reach the observer's direction. The observed Gamma-rays below 5 MeV from this pulsar may be synchrotron radiation of secondary electron-positron pairs produced outside the accelerating regions.

Ruderman, Malvin↗

Recent Solar-Proton Fluxes

The event-integrated fluences of energetic solar protons up to 2004 at the Earth have been determined and compared to previous data. The current solar cycle has been very active, and very large fluxes of solar protons have been observed that have had serious effects in the solar system and will have produced many radionuclides in the surfaces of meteorites. Such huge events are not expected again until about 2008 or 2009.

Reedy, R. C.↗

Environmental protection of the solar power satellite

This paper examines theoretically several features of the interactions of the Solar Power Satellite (SPS) with its space environment. The leakage currents through the kapton and sapphire solar cell blankets are calculated. At geosynchronous orbit, this parasitic power loss is only 0.7%, and is easily compensated by oversizing. At low-earth orbit, the power loss is potentially much larger (3%), and anomalous arcing is expected for the high-voltage negative surfaces. Preliminary results of a three-dimensional self-consistent plasma and electric field computer program are presented, confirming the validity of the predictions made from the one-dimensional models. Lastly, the paper proposes magnetic shielding of the satellite, to reduce the power drain and to protect the solar cells from energetic electron and plasma ion bombardment. It is concluded that minor modifications from the baseline SPS design can allow the SPS to operate safely and efficiently in its space environment.

Reiff, P. H.↗

Global mesoscale variability from collinear tracks of SEASAT altimeter data

Eight to nine sets of global collinear altimeter data with a cross-track grid spacing of approximately 900 km at the equator and 600 km at midlatitude have been obtained from the last 25 days of the 1978 SEASAT mission. Since the geoid is time-invariant, such observations can reveal sea surface height variability caused by dynamic ocean phenomena. Variations due to deep ocean mesoscale features are presently solved for by eliminating the longer wavelength deviations, yielding sea height profiles with an accuracy of a few cm, and a global variability map constructed from these data which reveal an exceptionally realistic perspective of mesoscale energetics. The dominance of exceedingly small variability over extensive regions of the oceans is noted. In both the Atlantic and the Pacific, the North Equatorial Current systems were clearly expressed as zonal bands of higher variability.

Cheney, R. E.↗

Theoretical characterization of the reaction CH3 +OH yields CH3OH yeilds products: The (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO channels

The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty a" orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.

Walch, Stephen P.↗

Theoretical characterization of the reaction CH3 + OH yields CH3OH yields products - The (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO channels

The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty 'a' orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.

Walch, Stephen P.↗

The source of 90-day oscillations at Wake Island

Energetic 90-day oscillations of sea level have been intermittently observed at Wake Island in the western tropical Pacific during the past 2 decades. The oscillations tend to occur about 1.5 years after El Nino-Southern Oscillation events, to have amplitudes of 10-15 cm, and to persist for about 1 year. Sea surface heights from the Geosat altimeter are used to establish that these signals take the form of Rossby waves and have an energy source near the Big Island of Hawaii, which lies 40 deg of longitude to the east. Sea level and upper layer currents from an eddy-resolving numerical model are examined and suggest that the energy source is eddies generated off the Big Island of Hawaii. These eddies appear to be associated with westward currents that intermittently impinge on the island. Several alternate hypotheses are also discussed and rejected.

Mitchum, Gary T.↗

SAR observations in the Gulf of Mexico

The Gulf of Mexico (GOM) exhibits a wealth of energetic ocean features; they include the Loop Current with velocities of about 2 m/s and strong shear fronts, mesoscale eddies, double vortices, internal waves, and the outflow of the 'Mighty Mississippi' river. These energetic features can have a strong impact on the economies of the states surrounding the Gulf. Large fisheries, oil and gas production as well as pollution transport are relevant issues. These circulation features in the Gulf are invisible to conventional IR and visible satellite imagery during the Summer months due to cloud cover and uniform surface temperatures. Synthetic Aperture Radar (SAR) imagery of the Gulf does penetrate the cloud cover and shows a rich assembly of features there year-round. Below are preliminary results from GOM SAR imagery taken by SEASAT in 1978 and by the AIRSAR program in 1991.

Sheres, David↗

Geosat-derived sea level and surface current anomalies in the equatorial Pacific during the 1986-1989 El Nino and La Nina

Equatorial wave dynamics are essential in most oceanic models for reproducing aspects of the El Nino-Southern Oscillation (ENSO) phenomenon. Observational evidence of first baroclinic equatorial Kelvin and first symmetric meridional Rossby waves is found in Geosat-derived sea level anomalies (SLA) and surface zonal current anomalies (ZCA) in the equatorial Pacific ocean during the 1986-1987 El Nino and the ensuing 1988-1989 La Nina. This was made possible after extensive quality control and specific processing of the recently improved Geosat geophysical data records pertaining to the 17-day Exact Repeat Mission. In particular, the processing was made so that the Geosat-derived ZCA best fit near-surface zonal currents from three equatorial moorings at 165 deg E, 140 deg W, and 110 deg W. The Geosat-derived SLA and ZCA are decomposed into first baroclinic equatorial Kelvin and gravest Rossby modes. The emphasis is then put on the chronology of the ZCA at the equator where the currents are the most energetic and where Kelvin and first symmetric Rossby waves explain most of the variance in ZCA, in similar proportion. The 1986-1987 El Nino is mostly characterized by a strong downwelling Kelvin wave in December 1986, a series of downwelling Kelvin waves in March-October 1987, and a strong upwelling Rossby wave in March-September 1987. These waves are consistent with wind forcing, and all give rise to notable eastward ZCA for almost an entire year. During El Nino-La Nina transition period there is the occurrence of two downwelling Rossby waves originating from the eastern Pacific at times of favorable wind forcing. These Rossby waves switch the basin-wide ZCA from eastward to westward, terminating the warm event. Then, the 1988-1989 La Nina shows the generation of a series of upwelling Kelvin waves which are clearly identified in March/April and September/October 1988. These upwelling Kelvin waves are apparently related to the enhencement of the trade wind in the western half of the basin. These waves maintain the basin-wide westward ZCA for more than a year, although the ZCA is slightly reduced ba front of upwelling Rossby waves in phase with the normal seasonal cycle. The Kelvin wave forcing and sign of kelvin wave contribution versus Rossby wave contribution to ZCA in the western Pacific are discussed, and we conclude that neither pleads in favor of the delayed action oscillator mechanism.

Delcroix, Thierry↗

Computed Potential Energy Surfaces and Minimum Energy Pathway for Chemical Reactions

Computed potential energy surfaces are often required for computation of such observables as rate constants as a function of temperature, product branching ratios, and other detailed properties. We have found that computation of the stationary points/reaction pathways using CASSCF/derivative methods, followed by use of the internally contracted CI method with the Dunning correlation consistent basis sets to obtain accurate energetics, gives useful results for a number of chemically important systems. Applications to complex reactions leading to NO and soot formation in hydrocarbon combustion are discussed.

Walch, Stephen P.↗