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At least 1,315 records · Page 73
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NASA NTRS1997

Mechanism for the Green Glow of the Upper Ionosphere

The generation of the green line of atomic oxygen by dissociative recombination of 02 plus occurs by the capture of an electron into a repulsive state of 02 followed by dissociation along another state of a different electronic symmetry. The two states are coupled together by mixed symmetry Rydberg states. Quantum chemical calculations give a rate coefficient at room temperature of (0.39 (+ 0.31 or -0.19)) x 10 exp -8 cubic centimeters per second. The quantum yield of excited oxygen is within the range deduced from ground, rocket, and satellite observations. The rate coefficients and yields are needed in models of the optical emission, chemistry, and energy balance of planetary ionospheres.

Guberman, Steven L.↗
NASA NTRS2000

Ionization Properties of Molecules Commonly Used for Plasma Processing of Semi-Conductors

Two types of processes are involved in plasma processing of semi-conductors. They are: plasma etching or cleaning and plasma deposition of the semi-conducting materials. For plasma etching of semi-conductors mostly halogen containing gases are used as additives to gases such as O2 and N2. For plasma deposition gases such as C2H2, SiH4, Si2H6 have been tested in the past. For an optimal performance of a reactor it is important to model the plasma. In this modeling effort electron impact excitation and ionization cross sections play a central role. For ionization balance calculations values of ionization cross sections are needed. Ion molecule reactions determine the ultimate composition of the plasma. Recently it has been discovered that the by products of many of these plasmas are per fluro hydrocarbons (PFCs) which are highly infrared absorbing species and have long life times in the atmosphere. They cause global warming. A lot of research is being pursued at the present time to find alternative molecules which do not produce global warming gases as the and product of the plasma processing reactor. There is also interest in the ionization and dissociative ionization properties of these molecules from the point view of the plasma abatement of the pollutant gases at the exhaust of the semi-conductor processing reactors. At the conference ionization and dissociative ionization properties of some of these molecules will be presented.

Srivastava, S. K.↗
NASA NTRS1998

Search for Interstellar Water in the Translucent Molecular Cloud Toward HD 154368

We report an upper limit of 9 x 10(exp 12)/sq cm on the column density of water in the translucent cloud along the line of sight toward HD 154368. This result is based on a search for the C-X band of water near 1240 A carried out using the Goddard High-Resolution Spectrograph (GHRS) of the Hubble Space Telescope. Our observational limit on the water abundance, together with detailed chemical models of translucent clouds and previous measurements of OH along the line of sight, constrains the branching ratio in the dissociative recombination of H3O(+) to form water. We find at the 3 sigma level that no more than 30% of dissociative recombinations of H3O(+) can lead to H2O. The observed spectrum also yielded high-resolution observations of the Mg II doublet at 1239.9 A and 1240.4 A, allowing the velocity structure of the dominant ionization state of magnesium to be studied along the line of sight. The Mg II spectrum is consistent with GHRS observations at lower spectral resolution that were obtained previously but allow an additional velocity component to be identified.

Spaans, Marco↗
NASA NTRS2000

A Model For The Burning of Teflon

Teflon has been identified as suitable material for use in oxygen-enriched atmospheres because of its low specific enthalpy of combustion that is, less than 1500 cal/gram. However, once ignited, Teflon burns in a heterogeneous reaction until total consumption or depletion of oxygen occurs. A model is developed for the burning of Teflon in pure, high-pressure oxygen, 3.4 to 68.9 MPa. The Teflon polymer chain dissociates via monomer units due to pyrolysis. These monomer units diffuse to the surface due to free convection. The model consists of coupled mass and energy balances for the polymer and an energy balance for the free convection of product gases. The model is used to obtain appropriate kinetic parameters for the dissociation and surface reactions. The model is validated against experimental measurements of Teflon discs supported on aluminum rods (2216) at oxygen pressures of 3.4, 6.8, 34.4, and 68.9 MPa. The model simulates the temperature distribution in the product gases above burning Teflon.

Waller, Jess M.↗
NASA NTRS2001

Sunlit Io Atmospheric [O I] 6300 A and the Plasma Torus

A large database of sunlit Io [O I] 6300A emission, acquired over the period 1990-1999, with extensive coverage of Io orbital phase angle phi and System III longitude lambda(sub III), exhibits significant long-term and short-term variations in [O I] 6300A emission intensities. The long-term average intensity shows a clear dependence on lambda(sub III), which establishes conclusively that the emission is produced by the interaction between Io's atmosphere and the plasma torus. Two prominent average intensity maxima, 70 deg to 90 deg wide, are centered at lambda(sub III) about 130deg. and about 295 deg. A comparison of data from October 1998 with a three-dimensional plasma torus model, based upon electron impact excitation of atomic oxygen, suggests a basis for study of the torus interaction with Io's atmosphere. The observed short-term, erratic [O I] 6300A intensity variations fluctuate approximately 20% to 50% on time scale of tens of minutes with less frequent fluctuations of a factor of about 2. The most likely candidate to produce these fluctuations is a time-variable energy flux of field-aligned nonthermal electrons identified recently in Galileo PLS data. If true, the short-term [O I] intensity fluctuations may be related to variable field-aligned currents driven by inward and outward torus plasma transport and/or transient high-latitude, field-aligned potential drops. A correlation between the intensity and emission line width indicates molecular dissociation may contribute significantly to the [O I] 6300A emission. The nonthermal electron energy flux may produce O(1-D) by electron impact dissociation of SO2 and SO, with the excess energy going into excitation of O and its kinetic energy. The [O I] 6300A emission database establishes Io as a valuable probe of the torus, responding to local conditions at Io's position.

Oliversen, Ronald J.↗
NASA NTRS1999

Fourier Transform Ultraviolet Spectroscopy of the A Pi-2(3/2) Direct Current X Pi-2(3/2) Transition of BrO

The first spectra of the A (2)Pi(sub 3/2) from X (2)Pi(sub 3/2) electronic transition of BrO using Fourier transform ultraviolet spectroscopy are obtained. Broadband vibrational spectra acquired at 298 +/- 2 K and 228 +/- 5 K, as well as high-resolution rotational spectra of the A from X 7,0 and 12,0 vibrational bands are presented. Wavenumber positions for the spectra are obtained with high accuracy, and cross section assignments are made, incorporating the existing literature. With 35 cm(exp -1) (0.40 nm) resolution the absolute cross section at the peak of the 7,0 band is determined to be (1.58 +/- 0.12) x 10(exp -17) sq cm/molecule at 298 +/- 2 K and (1.97 +/- 0.15) x 10(exp -17) sq cm/molecule at 228 +/- 5 K. BrO dissociation energies are determined with a graphical Birge-Sponer technique, using Le Roy-Bernstein theory to place an upper limit on the extrapolation. From the ground-state dissociation energy, D(sub o)" = 231.0 +/- 1.7 kJ/mol, the heat of formation of BrO(g) is calculated, del(sub f)H(0 K) = 133.7 +/- 1.7 kJ/mol and del(sub f)H(298.15 K) = 126.2 +/- 1.7 kJ/mol. Cross sections for the high-resolution 7,0 and 12,0 rotational peaks are the first to be reported. The band structures are modeled, and improved band origins, rotational constants, centrifugal distortion constants, and linewidths are determined. In particular, J-dependent linewidths and lifetimes are observed for the both the 7,0 and 12,0 bands.

Wilmouth, David M.↗
NASA NTRS1998

C2 Fragmentation Energy of C60 Revisited: Theory Disagrees with Most Experiments

Following our earlier work on the subject, we have carried out density functional theory (DFT) and second-order Moller-Plesset perturbation theory (MP2) calculations of the dissociation energy of the reaction C60 yields C58 + C2 using polarized basis sets and geometries optimized with DFT methods. The present theoretical results support an electronic fragmentation energy D(sub e) around 10-11 eV in disagreement with most experimental results that place the dissociation energy D(sub o) (including zero point energy) around 7-8 eV. The plausible errors remaining in the theoretical calculations are unlikely to account for this big difference (2-4 eV).

Boese, A. Daniel↗
NASA NTRS1994

Line Profile Measurements of Atomic Oxygen at 1300 A with a VUV Raman Shifter

We are currently developing an atomic oxygen diagnostic to study the degree of oxygen dissociation in ground-based facilities. The absorption of the (sub 3)P - (sup 3)S(sup 0) resonance triplet in the vacuum ultraviolet is a direct measure of the ground state number density of atomic oxygen. Although the integrated line strength is well known for these transitions, the line profile is not. We report the results of a series of experiments in which the line profile is measured in shock-heated oxygen. An ArF excimer laser and a hydrogen Raman shifter generate tunable VUV radiation at the resonance wavelength. The test gas is dissociated oxygen, generated in the Electric Arc Shock Tube (EAST) Facility at NASA-Ames Research Center. By measuring the absorption of known concentrations of atomic oxygen, we are able to study the absorption line profile. The results will serve as a calibration to apply this diagnostic in other flowfields.

Sharma, Surendra P.↗
NASA NTRS1994

Relativistic and Correlation Effects in CuH, AgH and AuH: Comparison of Various Relativistic Methods

The effects of relativity on the bond lengths, dissociation energies, and harmonic vibrational frequencies of the 1Epsilon(+) electronic ground states of the group IB hydrides CuH, AgH and AuH have been evaluated with a variety of ab initio methods. These properties were investigated with moderately-sized basis sets at the self-consistent field Hartree Fock (SCF HF) level and with second-order Moller-Plesset (MP2) perturbation theory for electron correlation. Comparisons were made between all-electron results using the nonrelativistic Hamiltonian, perturbation theory (PT) at first-order with only the one-electron non-fine structure terms of the Breit-Pauli Hamiltonian, the spin-free Douglas-Kroll (DK) transformed Dirac Hamiltonian and the untransformed Dirac Hamiltonian, and results using two sets of relativistic effective core potentials (RECPs). The expected trends of bond length decrease, dissociation energy increase and harmonic frequency increase with both relativity and correlation are found. Both sets of RECPs are shown to give good results, if accompanied by a reasonable basis set. The DK method is demonstrated to be an inexpensive, reliable approximation to the DHF method.

Collins, Charlene L.↗
NASA NTRS2000

Charge Generation and Propagation in Igneous Rocks

Resistivity changes, ground potentials, electromagnetic (EM) and luminous signals prior to or during earthquakes have been reported, in addition to ground uplift and tilt, and to changes in the seismic wave propagation parameters. However, no physical model exists that ties these diverse phenomena together. Through time-resolved impacts experiments it has been observed that, when igneous rocks (gabbro, diorite, granite) are impacted at low velocities (approx. 100 m/sec), highly mobile electronic charge carriers are generated, spreading from a small volume near the impact point, causing electric potentials, EM and light emission. The rock becomes momentarily conductive. When impacted at higher velocities (approx. 1.5 km/sec), the propagation of the P and S waves is registered through the transient piezoelectric response of quartz. At the same time, the rock volume is filled with mobile charge carriers, and a positive surface potential is registered. During the next 1-2 msec the surface potential oscillates, due to electron injection from ground. These observations are consistent with positive holes, e.g. defect electrons in the O(2-) sublattice, that can travel via the O 2p-dominated valence band of the silicate minerals at the speed of a phonon-mediated charge transfer. Before activation, the positive hole charge carriers lay dormant in form of positive hole pairs, PHP, electrically inactive, chemically equivalent to peroxy links in the structures of constituent minerals. PHPs are introduced by way of hydroxyl (O3Si-OH) incorporated into nominally anhydrous minerals when they crystallize in water-laden environments. Given that sound waves of even relatively low intensity appear to cause PHPs dissociation, thus generating mobile positive holes, it is proposed that microfracturing during rock deformation cause PHP dissociation. Depending on where and how much the rock volume is stressed, the positive holes are expected to form fluctuating charge clouds in the earthquake source region that may account for earthquake-related electrical phenomena and the reported low frequency EM signals.

Freund, Friedemann↗
NASA NTRS1995

Rotational And Rovibrational Energy Transfer In Electron Collisions With Molecules

Air flows around a hypervelocity reentry vehicle undergo dissociation, rovibrational excitation and ionization. More specifically the air, initially 80% N2 and 20% O2, in the shock layer consists of species such as N, O, N2, O2, NO, N+, O+, N+, O+, NO+ and 2 free electrons. It was pointed out in multi temperature models'' that the temperature of the rotational energy modes and the gas-kinetic translational temperature are quickly equilibrated by a few collisions and rise rapidly to high temperatures as 50000K before falling off to equilibrium value of 10000K. Contrary, the electronic and vibrational temperatures state energy distributions remain low (less than 15000K) because of the slow equilibration. Electron vibrational energy transfer is thought to play a crucial role in such a ionizing flow regime since chemical reaction rates and dissociation depend strongly on the vibrational temperatures. Modeling of these flowfields in principle require the rovibrational excitation and de-excitation cross section data for average electron energies from threshold up to several eV (leV=11605.4 K). In this lecture we focus on theoretical description of rotational effects i.e. energy transfer of electrons to molecules such that the molecular rotational (vojo goes to voj) or vibrational and rotational (v(sub 0)j(sub 0) goes to vj) states are changed. Excitation and de-excitation of electronic states was discussed in a previous talk at this conference.

Thuemmel, Helmar T.↗
NASA NTRS1998

A Comparison of ZnO and ZnO(-)

Ab initio electronic structure calculations are performed to support and to help interpret the experimental work reported in the proceeding manuscript. The CCSD(T) approach, in conjunction with a large basis set, is used to compute spectroscopic constants for the X(exp 1)Epsilon(+) and (3)II states of ZnO and the X(exp 2)Epsilon(+) state of ZnO(-). The spectroscopic constants, including the electron affinity, are in good agreement with experiment. The ZnO EA is significantly larger than that of O, thus relative to the atomic ground state asymptotes, ZnO(-) has a larger D(sub o) than the (1)Epsilon(+) state, despite the fact that the extra electron goes into an antibonding orbital. The changes in spectroscopic constants can be understood in terms of the X(exp 1)Epsilon(+) formally dissociating to Zn (1)S + O (1)D while the (3)II and (2)Epsilon(+) states dissociate to Zn (1)S + O (3)P and Zn (1) and O(-) (2)P, respectively.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1998

Flow Characteristics of UHV Nitrogen Arcjet

Flow characteristics in the nozzle of a nitrogen arcjet have been simulated by a model. Electrons, ions, and neutral atoms and molecules are represented as separate species. Dissociation, ionization, and recombination are treated as separate reactions. Thermal non-equilibrium is represented by a two-temperature model. Energy input to plasma from the arc is modeled as a source determined by local current and electrical conductivity. Momentum and energy losses and recombinations at the nozzle wall are included as source/sink determined by fluxes to the wall. The results show essentially frozen gas-phase reactions and thermal nonequilibrium due to Joule heating of electrons and in the expansion part of the nozzle. Wall interactions have strong effects on the results, indicating that they play important roles in the flow due to very high surface area relative to the volume of the plasma. For example, plasma velocity decreases from 6000 m per s without wall interactions to 3000 m per s with modest amount of wall interactions. These results also show reasonable agreement with optical emission measurements, which confirms that the arcjet plasma is far from LTE. The spectra suggest nitrogen dissociation levels of 0.3% - 9%, depending on nitrogen flow rate and arc plasma current, which also determine the relative amounts of excited atomic and molecular nitrogen. Langmuir probe studies of the source show that electron and ion fluxes increase with increasing power, and that the ion energy distribution shifts to lower energies. Typical ion fluxes were on the order of 4E-9 A/cm**2 with a maximum ion kinetic energy of 3.5eV. The median electron energy was 1eV, with a maximum of less than 4eV.

Chang, C. H.↗
NASA NTRS2002

Photodissociation of Peroxynitric Acid in the Near-IR

Temperature-dependent near-IR photodissociation spectra were obtained for several vibrational overtone transitions of peroxynitric acid (HNO4) with a tunable OPO photolysis/OH laser-induced-fluorescence system. Band-integrated photodissociation cross-sections (definity integral of sigma(sub diss)), determined relative to that for the 3nu(sub 1), OH stretching overtone, were measured for three dissociative bands. Assuming unit quantum efficiency for photodissociation of 3nu(sub 1), we find 2nu(sub 1) + nu(sub 3)(8242/cm) = (1.21 x 10(exp -20) (independent of temperature), 2nu(sub 1) (6900/cm) = 4.09 x 10(exp 18) * e(sup (-826,5/T)) (295 K greater than T greater than 224 K), and nu(sub 1) + 2nu(sub 3) (6252/cm) = 1.87 x 10(exp -19) * e(sup (- 1410.7/T)) (278 K greater than T greater than 240 K) sq cm/molecule cm. The photodissociation cross-sections are independent of pressure over the range 2 to 40 Torr. Temperature-dependent quantum yields (phi) for these transitions were obtained using integrated absorption cross-sections (definity integral of sigma(sub abs)) of HNO4 overtone vibrations measured with a FTIR spectrometer. In the atmosphere, photodissociation in the infrared is dominated by excitation of the first overtone of the OH stretching vibration (2nu((sub 1)). Inclusion of all dissociative HNO4 overtone and combination transitions yields a daytime IR photolysis rate of approximately 1 x 10(esp -1)/s. This process significantly shortens the estimated lifetime of HNO4 in the upper troposphere and lower stratosphere.

Roehl, Coleen M.↗
NASA NTRS2002

Measurements of [C I] 9850 A Emission from Comet Hale-Bopp

We present quantitative measurements of cometary [C I] 9850 A, emission obtained during observations of comet Hale-Bopp (C/1995 O1) in 1997 March and April. The observations were carried out using a high-resolution (lambda/Delta lambda approx. 40,000) Fabry-Perot/CCD spectrometer at the McMath-Pierce solar telescope on Kitt Peak. This forbidden line, the carbon analog of [O I] 6300 A, is emitted in the radiative decay of C(1D) atoms. In the absence of other sources and sinks, [C I] 9850 A emission may be used as a direct tracer of CO photodissociation in comets. However, in Hale-Bopp's large, dense coma, other processes, such as collisional excitation of ground-state C(3P), dissociative recombination of CO+, and collisional dissociation of CO and CO2 may produce significant amounts of C(1D). The long C(1D) radiative lifetime (approx. 4000 s) makes collisional de-excitation (quenching) the primary loss mechanism in the inner coma. Thus, a detailed, self-consistent global model of collisional and photochemical interactions is necessary to fully account for [C I] 9850 A emission in comet Hale-Bopp.

Oliversen, R. J.↗
NASA NTRS2003

The Shock Structure of Supernova Remnant IC443

We present and discuss ISO observations of IC443, a supernova remnant interacting with a molecular cloud. An SWS spectrum centered on molecular hydrogen clump R10E (RA(2000) = 6 17 7.6, Decl(2000) = 22 25 34.6) is dominated by strong [SiII] (34 microns) emission and the pure rotational transitions of molecular hydrogen ranging from 0-0 S(1) to 0-0 S(13). Fits to these H$-2$ lines imply a large column (approx. 7E19 cm$ {-2)$) of warm (T approx. 700 K) gas and an ortho/para ratio for hydrogen near 3. LWS Fabry-Perot spectra of [OI] (63 microns) and [CII] (158 microns) at positions R10E and C (RA(2000) = 6 17 42.8, Decl(2000) = 22 21 38.1) find broad (approx. 75 km/s), blue-shifted (-40 km/s) line profiles; their similarity strongly suggests a common, shock-generated origin for these two lines. The surprisingly large [CII]/[OI] ratio (approx. 0.1 to 0.2) confirms previous observations with the Kuiper Airborne Observatory. These [CII] and [OI] line intensities, the [SiII] intensity (above), and LWS grating measurements of OH (119 microns) and [OI] (145 microns) are all readily fit by a single, fast J-shock model. Although the [OI] (63) emission can alternatively be produced by a slow C-shock, this ensemble of lines can not be produced by such a shock and provides strong evidence for the existence of a J-shock. A 24-arcmin strip map shows that this far-infrared line emission is spatially correlated with the H$-2$ 1-0 S(1) emission, which most likely arises in an associated C-shock. In addition to this spatially correlated shock emission, the strip map identifies extended [CII] and [OI] emission with a significantly larger line ratio (approx. 0.6); this 'background' component is compared with current J-shock, C-shock, photo-dissociation region (PDR), and X-ray dissociation region (XDR) models in an effort to explain its origin.

Haas, Michael R.↗
NASA NTRS1958

Extreme Speeds and Thermodynamic States in Supersonic Flight

The increasing importance of high-speed flow leads to similar problems in various fields of research which are summarized in what follows. Typical of all cases is the conversion of high kinetic energy into extreme thermodynamic states with temperatures of several thousand degrees, frequently connected with dissociation and ionization of the gas involved. There is also a characteristic small sensitivity to the processes discussed in the case of gases of low molecular weight (light gases). The penetration of meteors into the atmosphere of the earth at astronomical speeds results in temperatures higher than those of the surface of the sun. Such temperatures may be produced in shock tubes, with light gases used as the driving gas. For supersonic fighters the problem of propulsion is less difficult to solve than the problem of large heating, on the surface and in the combustion chamber. Finally, for the space-travel rocket, astronomical speeds have to be reached which require the lightest possible gases as propellants. Here again, dissociation processes in the combustion chamber are of considerable importance.

Oswatitsch, Klaus↗
NASA NTRS2004

The Influence of Solar Proton Events in Solar Cycle 23 on the Neutral Middle Atmosphere

Solar proton events (SPEs) can cause changes in constituents in the Earth's middle atmosphere. The highly energetic protons cause ionizations, excitations, dissociations, and dissociative ionizations of the background constituents, which lead to the production of HO(x) (H, OH, HO2) and NO(y) (N, NO, NO2, NO3, N2O5, HNO3, HO2NO2, ClONO2, BrONO2). The HO(x) increases lead to short-lived ozone decreases in the mesosphere and upper stratosphere due to the short lifetimes of the HO, constituents. The NO(x) increases lead to long-lived stratospheric ozone changes because of the long lifetime of NO(y) constituents in this region. Solar cycle 23 was quite active with SPEs and very large fluxes of high energy protons occurred in July and November 2000, November 200 1, and April 2002. Smaller, but still substantial, proton fluxes impacted the Earth during other months in the 1997-2003 time period. The impact of the very large SPEs on the neutral middle atmosphere during solar cycle 23 will be discussed, including the HO(x), NO(y), ozone variations and induced atmospheric transport changes. Two multi-dimensional models, the Goddard Space Flight Center (GSFC) Two-dimensional (2D) Model and the Thermosphere Ionosphere Mesosphere Electrodynamic General Circulation Model (TIME-GCM), were used in computing the influence of the SPEs. The results of the GSFC 2D Model and the TIME-GCM will be shown along with comparisons to the Upper Atmosphere Research Satellite (UARS) Halogen Occultation Experiment (HALOE) and Solar Backscatter Ultraviolet 2 (SBUV/2) instruments.

Jackman, Charles H.↗