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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 181 records · Page 10
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NASA NTRS1984

The dissociation of OH and OD in comets by solar radiation

Calculations of the radiative lifetimes of cometary OH are presented as a function of the radial velocity of the comet and of the velocity distributions of the hydrogen and oxygen atoms produced by photodissociation of OH. The contribution of the photodissociation of OH to the emission of the red and green lines of atomic oxygen is assessed. An estimate is made of the lifetime of OD and of the velocity distribution of the deuterium atoms.

Van Dishoeck, E. F.↗
NASA NTRS1985

Design and chemical synthesis of iodine-containing molecules for application to solar-pumped I* lasers

This work is directed toward the design and chemical synthesis of new media for solar-pumped I* lasers. In view of the desirability of preparing a perfluoroalkyl iodide absorbing strongly at 300 nm, the relationship betwen perfluoroalkyl iodide structure and the corresponding absorption wavelength was reexamined. Analysis of existing data suggests that, in this family of compounds, the absorption maximum shifts to longer wavelength, as desired, as the C-I bond in the lasant is progressively weakened. Weakening of the C-I bond correlates, in turn, with increasing stability of the perfluoroalkyl radical formed upon photodissociation of the iodide. The extremely promising absorption characteristics of perfluoro-tert-butyl iodide can be accounted for on this basis. A new technique of diode laser probing to obtain precise yields of I* atoms in photodissociation was also developed.

Shiner, C. S.↗
NASA NTRS1985

A model for the CI (609 micron) emission of Orion

A numerical model energy balance and chemical equilibrium in the photodissociation regions at the edge of molecular clouds is presented. The model is used to calculate the emergent intensities of the following fine-structure lines: OI (at 63, 145 microns); CI (at 609, 370 microns); C II (at 158 microns); and the low-lying rotational transitions of CO. It is shown that column densities in the range 2 x 10 to the 17th to 2 x 10 to the 18th per sq cm can be obtained for the C(+)/C/CO transition region at the edges of molecular clouds. The difference in the column densities is attributed to changes in the charge exchange reactions of C(+) with SiO and S, and to the process of carbon self-healing. It is found that the calculations are in good agreement with the observed conditions in the photodissociation regions behind Orion (1) C Ori, and near the surface of OMC 1.

Tielens, A. G. G. M.↗
NASA NTRS1985

The internal state distribution of CN radicals produced in the photolysis of HC2CN and CH3CN

The energy partitioning in CN radicals produced by the vacuum ultraviolet photodissociation of HC2CN and CH3CN is studied by means of laser-induced fluorescence of the B-X transition. Experiments are performed in two collision regimes: (1) in the low-collision number regime, the energy partitioning in CN(X) is measured; (2) in the high-collision number regime, the formation of CN(A) is monitored. It is shown that photodissociation of HC2CN in its linear predissociative 1Sigma(+) state produces predominantly ground-state CN in rotationally and vibrationally excited states. The vibrational population ratios and the temperatures computed from a Boltzmann fit of the rotational levels are given in a table. The excitation of CH3CN produces CN radicals almost entirely in the first excited A-state with vibrational excitation.

Cody, R. J.↗
NASA NTRS1985

Detection of [SiLL] (34.8 micron) emission in Orion-KL: A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows SiII emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x to the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density approx. 10 to the 3/cc cloud toward zeta Oph. The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited SiII (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗
NASA NTRS1985

Accurate quantum yields by laser gain vs absorption spectroscopy - Investigation of Br/Br(asterisk) channels in photofragmentation of Br2 and IBr

Various techniques have been used to study photodissociation dynamics of the halogens and interhalogens. The quantum yields obtained by these techniques differ widely. The present investigation is concerned with a qualitatively new approach for obtaining highly accurate quantum yields for electronically excited states. This approach makes it possible to obtain an accuracy of 1 percent to 3 percent. It is shown that measurement of the initial transient gain/absorption vs the final absorption in a single time-resolved signal is a very accurate technique in the study of absolute branching fractions in photodissociation. The new technique is found to be insensitive to pulse and probe laser characteristics, molecular absorption cross sections, and absolute precursor density.

Haugen, H. K.↗
NASA NTRS1986

Detection of (Si II) (34.8 micron) emission in Orion-KL - A measurement of the silicon abundance in dense interstellar gas

The first detection of the ground state fine structure transition of Si+ at a rest wavelength determined to be 34.815 + or - 0.004 micron are reported. These observations were obtained with the facility spectrometer on NASA's Kuiper Airborne Observatory. A 6' NW-SE strip scan across the Orion-KL region shows Si II emission from both the extended photodissociation region surrounding theta 1 Ori C and from the shocked gas NW of BN-KL. The inferred gas-phase silicon elemental abundance relative to hydrogen in the dense 10 to the 5/cc primarily neutral photodissociation region is approximately 2.6 x 10 the -6, a factor of 0.075 times the solar value and 3.4 times greater than the abundance in the moderate density aprox. 10 to the 3/cc cloud toward Zeta Oph The silicon abundance in the shocked gas is approximately solar, indicating that any pre-existing grains have been destroyed in the shock wave or that the preshock gas carries a near solar abundance of gas phase silicon. The shock-excited Si II (34.8 micron) emission may arise from shocked wind material in the outflow around IRc2, with wind velocities approx. 100 km/s.

Haas, M. R.↗
NASA NTRS1990

Warm dense gas in the reflection nebula NGC 2023

A photodissociation region (PDR) with a known UV excitation source was studied by examining emission from atomic and molecular material. In agreement with models of externally excited PDRs, the photodissociation region southwest of HD 37903 contains both atomic and excited molecular material and arises close to the exciting star than does the bulk of the molecular cloud. The C(+) emission arises closest to the star but is 1.5 x 10 to the 17th cm or less from the peaks in the excited CO and fluorescent H2 emission regions. The (C-18)O J = 2 - 1 line, which traces molecular column density, has its emission peak about 4 x 10 to the 17th cm beyond the C(+) peak. Even in a source with an incident UV flux as low as about 1000 times the mean interstellar radiation field, there is a significant amount of CO 7 - 6 emission arising from regions with T(gas) greater than 85 K which is substantially greater than T(dust).

Jaffe, D. T.↗
NASA NTRS1990

A comparison of UV surface brightness and HI surface densities for spiral galaxies

Shaya and Federman (1987) suggested that the ambient ultraviolet flux at 1000 A permeating a spiral galaxy controls the neutral hydrogen (HI) surface density in the galaxy. They found that the atomic envelopes surrounding small molecular clouds, because of their great number, provide the major contribution to the HI surface density over the stellar disk. The increase in HI surface density with later Hubble types was ascribed to the stronger UV fields from more high-mass stars in later Hubble types. These hypotheses are based on the observations of nearby diffuse interstellar clouds, which show a sharp atomic-to-molecular transition (Savage et al. 1977), and on the theoretical framework introduced by Federman, Glassgold, and Kwan (1979). Atomic envelopes around interstellar clouds in the solar neighborhood arise when a steady state is reached between photodissociation of H2 and the formation of H2 on grains. The photodissociation process involves photons with wavelengths between 912 A and 1108 A. Shaya and Federman used H-alpha flux as an approximate measure for the far UV flux and made their comparisons based on averages over Hubble type. Here, researchers compare, on an individual basis, UV data obtained with space-borne and balloon-borne instruments for galaxies with measurements of HI surface density (Warmels 1988a, b). The comparisons substantiate the conclusion of Shaya and Federman that the far UV field controls the HI content of spiral galaxies.

Federman, S. R.↗
NASA NTRS1990

A status report on the analysis of the NOAA-9 SBUV/2 sweep mode solar irradiance data

Monitoring of the near ultraviolet (UV) solar irradiance is important because the solar UV radiation is the primary energy source in the upper atmosphere. The solar irradiance at wavelengths shortward of roughly 300 nm heats the stratosphere via photodissociation of ozone in the Hartley bands. Shortward of 242 nm the solar UV flux photodissociates O2, which is then available for ozone formation. Upper stratosphere ozone variations coincident with UV solar rotational modulation have been previously reported (Gille et al., 1984). Clearly, short and long term solar irradiance observations are necessary to separate solar-forced ozone variations from anthropogenic changes. The SBUV/2 instrument onboard the NOAA-9 spacecraft has made daily measurements of the solar spectral irradiance at approximately 0.15 nm intervals in the wavelength region 160-405 nm at 1 nm resolution since March 1985. These data are not needed to determine the terrestrial ozone overburden or altitude profile, and hence are not utilized in the NOAA Operational Ozone Product System (OOPS). Therefore, assisted by the ST System Corporation, NASA has developed a scientific software system to process the solar sweep mode data from the NOAA-9 instrument. This software will also be used to process the sweep mode solar irradiance data from the NOAA-11 and later SBUV/2 instruments. An overview of the software system and a brief discussion of analysis findings to date are provided. Several outstanding concerns/problems are also presented.

Cebula, R. P.↗
NASA NTRS1991

Formation of ions and radicals from icy grains in comets

Ion and radical formation in comets are thought to occur primarily by photodissociation of gas phase molecules. Experimental evidence and theoretical calculations are presented that show that some of the radical and ions can come directly from ice grains. The experimental evidence suggest that if the frozen molecules on the surface of grains undergo direct dissociation then they may be able to release radicals directly in the gas phase. If the molecules undergo predissociation it is unlikely that they will release radicals in the gas phase since they should be quenched. Calculations of this direct photodissociation mechanism further indicate that even if the parent molecule undergoes direct dissociation, the yield will not be high enough to explain the rays structure in comets unless the radicals are stored in the grains and then released when the grain evaporates. Calculations were also performed to determine the maximum number of ions that can be stored in an icy grain's radius. This number is compared with the ratio of the ion to neutral molecular density. The comparison suggests that some of the ions observed near the nucleus of the comet could have originally been present in the cometary nucleus. It is also pointed out that the presence of these ions in icy grains could lead to radical formation via electron recombination. Finally, an avalanche process was evaluated as another means of producing ions in comets.

Jackson, William M.↗
NASA NTRS1991

A determination of Mg(+)-ligand binding energies

Theoretical calculations employing large basis sets and including correlation are carried out for Mg(+) with methanol, water, and formaldehyde. For Mg(+) with ethanol and acetaldehyde, the trends in the binding energies are studied at the self-consistent-field level. The predictions for the binding energy of Mg(+) to methanol and water of 41 + or - 5 and 36 + or - 5 kcal/mol, respectively, are much less than the experimental upper bounds, of 61 + or - 5 and 60 + or - 5 kcal mol, determined by using photodissociation techniques. The theoretical results are inconsistent with the onset of Mg(+) production observed in the photodissociation experiments, as the smallest absorptions are calculated at about 80 kcal/mol for both Mg(+)-CH3OH and Mg(+)-H2O, and these transitions are to bound excited states. The binding energy for Mg(+) with formaldehyde is predicted to be similar to Mg(+)-H2O. The relative binding energies are in reasonable agreement with experiment. The binding energy of a second water molecule to Mg(+) is predicted to be similar to the first. This suggests that the reduced reaction rate observed for the second ligand is not a consequence of a significantly smaller binding energy, at least for the smaller ligards such as those considered in this work.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1991

Neutral matter in planetary nebulae

A review of current studies of neutral envelopes is presented with particular attention given to the use of the envelopes as test cases for understanding the ionization and thermal structure of photodissociation regions. The study of near-IR H2 emission is discussed with detailed spectra given for a few planetary nebulae, and airborne observations of far-IR atomic lines are discussed. These two methods can discern photodissociation regions with warm gas and UV flux is fairly prominent. The use of resonance-absorption-line spectroscopy is also reviewed with respect to the analysis of the Na D lines, and thereby allows the measurement of integrated columns of material through the shell. The methods provide evidence for the notion that planetary nebulae consist of more than just ionized material; large amounts of neutral and molecular material are being confirmed, which has important implications for the mass-loss episode of the nebulae.

Dinerstein, Harriet L.↗
NASA NTRS1991

Production of N(+)-asterisk from N2 + hnu - Effective EUV emission yields from laboratory and dayglow data

Photodissociative ionization of N2 into the unbound N2(+) H 2Sigma-g(+) state is identified as the parentage of a number of N(+) and N-excited states that contribute to the u.v. dayglow. Yields have been obtained for the production of extreme ultraviolet emission lines of N(+) and N from a laboratory experiment using a broadband synchrotron radiation source with fluorescence spectroscopy. The yields are termed 'effective', in that they are constant percentages of the H state cross section. These are compared wih effective yields needed to reproduce N II 1085 and 916 A lines from four dayglow observations using a model of solar energy deposition and photoelectron production and loss in the earth's thermosphere. The 1085 A effective yield measured in the laboratory (18 percent) agrees with that from the dayglow data (average of 17 percent) to well within experimental uncertainties. Thus, it is concluded that photodissociative ionization of N2 is the primary source of the N II 1085 A dayglow. However, there is an order of magnitude discrepancy among the various dayglow observations of the 1085/916 intensity ratio, only one of which is consistent with the laboratory observation of 4.4. Neither contamination by other dayglow features nor atmospheric extinction can account for the disparities. Laboratory measurements of N2 and O2 absorption cross sections at these wavelengths are also reported.

Meier, R. R.↗
NASA NTRS1993

The case of missing CO-13 in mergers

We present a comparison of the CO-13 and CO-12 emissions of six systems of merging galaxies: NGC 828, NGC 3256, NGC 4194, NGC 6240, Arp 220, and Arp 299. The observations were made in both J=1-0 and J=2-1 transitions with the IRAM 30 m and SEST 15 m telescopes. In all galaxies but NGC 828, the CO-13 is much weaker than in spiral galaxies. The average emissivity ratios measured at the few kiloparsec scale are: CO-12(1-0)/CO-13(1-0) approx. equals 30, CO-12(2-1)/CO-13(2-1) approx. equals 40. These values are significantly larger than those usually measured in normal spiral galaxies, which are always between 5 and 15 for the J=1-0 line. We show that such a peculiar behavior cannot be interpreted as due to the dominant presence of diffuse gas and it cannot be attributed to optically thin CO emission either. The faint CO-13 emission of mergers must result from either an underabundance of CO-13 or an overabundance of CO-12. They may be accounted for by different mechanisms: CO-13 molecules are more easily photodissociated than CO-12 ones - however our observations seem to rule out physical conditions characteristic of photodissociation regions; in the course of the merging, large amounts of unprocessed gas, with a high (CO-12/CO-13) abundance ratio, are driven from the external regions of the progenitor galaxies to the new nucleus - this could increase the (CO-12/CO-13) ratio by a factor of 2; the interstellar medium can also be quickly enriched in C-12 (thus in CO-12) by a factor of 2, due to selective nucleosynthesis of this isotope (vs. C-13) in the massive stars born during the starburst. The last two processes can thus significantly contribute to the weakness of the CO-13 lines. The high CO-13-to-CO-12 line ratios that we have measured are due to the deep transformations that take place in the interstellar medium during the merging and the starburst: indeed, the only object with nearly normal line ratios, NGC 828, appears less perturbed and active in star formation than the other sources in the sample. In most mergers, the faintness of the CO-13 emission may indicate that the conversion factor from CO-12 emissivities to H2 column densities could differ substantially from the standard galactic value.

Casoli, Fabienne↗
NASA NTRS1993

Molecular processes in comets

A major effort was expended in developing procedures for calculating by quantum-mechanical methods the cross sections for the photodissociation of the hydroxyl radical OH. The molecule OH is the primary dissociation product of water and observations of OH when combined with a determination of the lifetime of OH in the solar radiation field can be used to calculate the rate of release of water from comets. There are many possible photodissociation channels whose efficiency depends upon the details of the spectrum of the radiation. We have calculated the potential energy curves of all the states of OH that can be reached by electric dipole absorption from the ground X(exp 2)(Pi) state by photons with energies up to about 12 eV.

Dalgarno, A.↗
NASA NTRS1992

Direct observation of ClO from chlorine nitrate photolysis

Chlorine nitrate photolysis has been investigated with the use of a molecular beam technique. Excitation at both 248 and 193 nanometers led to photodissociation by two pathways, ClONO2 yields ClO + NO2 and ClONO2 yields Cl + NO3, with comparable yields. This experiment provides a direct measurement of the ClO product channel and consequently raises the possibility of an analogous channel in ClO dimer photolysis. Photodissociation of the ClO dimer is a critical step in the catalytic cycle that is presumed to dominate polar stratospheric ozone destruction. A substantial yield of ClO would reduce the efficiency of this cycle.

Minton, Timothy K.↗
NASA NTRS1994

Temperature dependence of ultraviolet absorption cross-sections of alternative hydrochlorofluorocarbons

Ultraviolet absorption cross-section of six alternative hydrochlorofluorocarbons (HCFC-21 HCFC-22, HCFC-123, HCFC-124, HCFC-141b and HCFC-142b1) have been measured between 170 and 260 nm for temperature ranging from 210 to 295 K. These data are compared with other available determinations performed at room temperature and their temperature dependence is discussed. Photodissociation coefficients are estimated and their temperature dependence is discussed. Impact of the photodissociation on the total atmospheric destruction of these compounds is illustrated.

Gillotay, D.↗