Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Photodissociation”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 703 records · Page 39

Ozone Depletion, UVB and Atmospheric Chemistry

The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

Stolarski, Richard S.↗

Ozone Depletion, UVB and Atmospheric Chemistry

The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

Stolarski, Richard S.↗

Heterogeneous Chemistry of HONO on Liquid Sulfuric Acid: A New Mechanism of Chlorine Activation on Stratospheric Sulfate Aerosols

Heterogeneous chemistry of nitrous acid (HONO) on liquid sulfuric acid (H2SO4) Was investigated at conditions that prevail in the stratosphere. The measured uptake coefficient (gamma) of HONO on H2SO4 increased with increasing acid content, ranging from 0.03 for 65 wt % to about 0.1 for 74 wt %. In the aqueous phase, HONO underwent irreversible reaction with H2SO4 to form nitrosylsulfuric acid (NO(+)HSO4(-). At temperatures below 230 K, NO(+)HSO4(-) was observed to be stable and accumulated in concentrated solutions (less than 70 wt % H2SO4) but was unstable and quickly regenerated HONO in dilute solutions (less than 70 wt %). HCl reacted with HONO dissolved in sulfuric acid, releasing gaseous nitrosyl chloride (ClNO). The reaction probability between HCl and HONO varied from 0.01 to 0.02 for 60-72 wt % H2SO4. In the stratosphere, ClNO photodissociates rapidly to yield atomic chlorine, which catalytically destroys ozone. Analysis of the laboratory data reveals that the reaction of HCl with HONO on sulfate aerosols can affect stratospheric ozone balance during elevated sulfuric acid loadings after volcanic eruptions or due to emissions from the projected high-speed civil transport (HSCT). The present results may have important implications on the assessment of environmental acceptability of HSCT.

Zhang, Renyi↗

A New Probe of the Molecular Gas Content in Galaxies: Application to M101

Studies of nearby spiral galaxies suggest that photodissociation regions (PDRs) are capable of producing the observed large--scale distribution of HI (Allen et al.- 1997, and references therein). The column density of HI in a PDR is fundamentally linked to the amount of far--ultraviolet (FUV) emission produced by nearby young stars and the local molecular gas volume density. Measurements of the HI column density and the FUV emission associated with PDRs thus provide a new probe of the molecular gas distribution in nearby galaxies. Advantages of this method include its insensitivity to assumptions about the CO/{\rm H2} conversion factor or the gas temperature. We discuss the application of this method to M101. The HI column density and FUV emission have been measured for 35 PDRs from VLA data (Braun 1997) and Ultraviolet Imaging Telescope data (Waller et al.-1997). We derive volume densities ranging from n-100 {\rm cm(exp -3)} in the central HI--poor regions of M101 to n -3000 {\rm cm(exp -3)} in the HI--rich periphery of the galaxy.

Smith, D. A.↗

A New Probe of the Molecular Gas Content in Galaxies: Application to M101

Recent studies of nearby spiral galaxies suggest that photodissoiation regions (PDRS) are capable of producing much of the observed HI in galaxy disks. In that case, measurements of the observed HI column density and the far-ultraviolet (FUV) photon flux responsible for the photodissociation process provide a new probe of the volume density of the local underlying molecular hydrogen. We develop the method and apply it to the giant Scd spiral M101. The HI column density and amount of FUV emission have been measured for a sample of 35 candidate PDRs located throughout the disk of M101 using the Very Large Array and the Ultraviolet Imaging Telescope. We find that, after correction for the known gradient of metallicity in the Interstellar Medium (ISM) of M101 and for the extinction of the ultraviolet emission, molecular gas with a narrow range of density from 30-1000/ cubic cm is found near star-forming regions at all radii in the disk of M101 out to a distance of 12 seconds approximately equals 26 kpc, close to the photometric limit of R(sub 25) approximately equals 13.5 seconds. In this picture, the ISM is virtually all molecular in the inner parts of M101. The strong decrease of the HI column density in the inner disk of the galaxy at R(sub G) < 10 kpc is a consequence of a strong increase in the dust-to-gas ratio there, resulting in an increase of the H(sub 2) formation rate on grains and a corresponding disappearance of hydrogen in its atomic form.

Smith, Denise A.↗

High Resolution UV Emission Spectroscopy of Molecules Excited by Electron Impact

Photodissociation via discrete line absorption into predissociating Rydberg and valence states is the dominant destruction mechanism of CO and other molecules in the interstellar medium and molecular clouds. Accurate values for the rovibronic oscillator strengths of these transitions and predissociation yields of the excited states are required for input into the photochemical models that attempt to reproduce observed abundances. We report here on our latest experimental results of the electron collisional properties of CO and N2 obtained using the 3-meter high resolution single-scattering spectroscopic facility at JPL.

James, G. K.↗

Red Fluorescent Line Emission from Hydrogen Molecules in Diffuse Molecular Clouds

We have modeled the fluorescent pumping of electronic and vibrational emissions of molecular hydrogen (H2) within diffuse molecular clouds that are illuminated by ultraviolet continuum radiation. Fluorescent line intensities are predicted for transitions at ultraviolet, infrared, and red visible wavelengths as functions of the gas density, the visual extinction through the cloud, and the intensity of the incident UV continuum radiation. The observed intensity in each fluorescent transition is roughly proportional to the integrated rate of H2 photodissociation along the line of sight. Although the most luminous fluorescent emissions detectable from ground-based observatories lie at near-infrared wavelengths, we argue that the lower sky brightness at visible wavelengths makes the red fluorescent transitions a particularly sensitive probe. Fabry-Perot spectrographs of the type that have been designed to observe very faint diffuse Ha emissions are soon expected to yield sensitivities that will be adequate to detect H2 vibrational emissions from molecular clouds that are exposed to ultraviolet radiation no stronger than the mean radiation field within the Galaxy. Observations of red H2 fluorescent emission together with cospatial 21 cm H I observations could serve as a valuable probe of the gas density in diffuse molecular clouds.

Neufeld, David A.↗

Molecular Hydrogen in Diffuse Interstellar Clouds of Arbitrary Three-Dimensional Geometry

We have constructed three-dimensional models for the equilibrium abundance of molecular hydrogen in diffuse interstellar clouds of arbitrary geometry that are illuminated by ultraviolet radiation. The position-dependent photodissociation rate of H2 in such clouds was computed with a 26 ray approximation to model the attenuation of the incident ultraviolet radiation field by dust and by H2 line absorption. We have applied our modeling technique to the isolated diffuse cloud G236+39, assuming that the cloud has a constant density and that the thickness of the cloud along the line of sight is at every point proportional to the 100 micron continuum intensity measured by IRAS. We find that our model can successfully account for observed variations in the ratio of 100 micron continuum intensity to H I column density, with larger values of that ratio occurring along lines of sight in which the molecular hydrogen fraction is expected to be the largest. Using a standard chi square analysis to assess the goodness of fit of our models, we find (at the 60 a level) that a three-dimensional model is more successful in matching the observational data than a one-dimensional model in which the geometrical extent of the cloud along the line of sight is assumed to be much smaller than its extent in the plane of the sky. If D is the distance to G236 + 39, and given standard assumptions about the rate of grain-catalyzed H2 formation, we find that the cloud has an extent along the line of sight that is 0.9 +/- 0.1 times its mean extent projected onto the plane of the sky and a gas density of 53 +/- 8 (100 pc/D) H nuclei/cc and is illuminated by a radiation field of 1.1 +/- 0.2 (100 pc/D) times the mean interstellar radiation field. The derived 100 micron emissivity per nucleon is 1.13 +/- 0.06 x 10(exp -20) MJy/sr sq cm.

Spaans, Marco↗

High-Resolution Spectroscopy of Mars: Recent Results and Implications for Atmospheric Evolution

It is believed that Earth, Venus, and Mars were formed by the same rocky and icy planetesimals, which resembled meteorites and comets in their composition, respectively. These planets are thus expected to have initially had the same chemical and isotope composition. Scaling the mass of the terrestrial ocean by the planetary mass ratio, the expected initial H2O abundance on Mars is a layer of about 1 km thick. Scaling the abundance of CO2 on Venus, the expected initial CO2 abundance on Mars is 15 bars. Evidently, significant parts of the initial H2O and CO2 abundances have been lost. Intense meteorite impact erosion and hydrodynamic escape of hydrogen (which could drag to escape more heavy species) were dominant loss processes in the first 0.8 Byr. Later, atmospheric sputtering by O+ ions resulted in the dissociation of CO2 and massive losses of O, C, and H. Formation of carbonates also reduced CO2 to its present abundance which currently exists in the atmosphere, on the polar caps, and is absorbed by regolith. Water loss is currently due to thermal escape of H and nonthermal escape of O, both formed by photodissociation of H2O. All loss processes resulted in fractionation of the H, O, and C isotopes. Therefore, the current isotope ratios in H2O and CO2 are clues to the history of volatiles on Mars. There are three tools to study H2O and CO2 isotopes in the martian atmosphere: (i) mass spectrometry from landing probes, (ii) analyses of Mars' gases trapped in the SNC meteorites which were ejected from Mars, and (iii) high-resolution spectroscopy of the H2O andCO2 bands. Method (i) is the best but is the most expensive. Mass spectrometers to be used should be designed for high-precision isotope measurements. Method (ii) makes it possible to reach an uncertainty +/- 0.1%. However, the obtained results are affected by some uncontrolled interactions: isotope fractionations of (1) trapped gases and (2) those released in pyrolysis, (3) contribution of the impactor, isotope exchanges (4) in the terrestrial environment and (5) with the host rock during pyrolysis. Therefore, the spectroscopic data are of great interest, though their formal accuracy is lower. High-resolution spectroscopy is also a tool to study the current atmosphere of Mars by mapping of some photochemically important species and searching for some minor constituents and their variations. Additional information is contained in the original extended abstract.

Krasnopolsky, V. A.↗

Unseeded Scalar Velocity Measurements for Propulsion Flows

Unseeded molecular tagging methods based on single-photon processes that produce long tag lines (>50 mm) have been recently developed and demonstrated by the Combustion Laser Diagnostics Group (Mechanical Engineering Department) at Vanderbilt University [1,2]. In Ozone Tagging Velocimetry (OTV) a line of ozone (O3) is produced by a single photon from a pulsed narrowband argon fluoride (ArF) excimer laser operating at - 193 nm. After a known time delay, t, the position of the displaced (convected in the flow field) O3 tag line is revealed by photodissociation of O3 and subsequent fluorescence of O2, caused by a pulsed laser sheet from a krypton fluoride (KrF) excimer laser operating at - 248 nm. Intensified CCD camera images of the fluorescence are taken from the initial and final tag line locations thus providing unobtrusive means of establishing a velocity profile in the interrogated flow field. The O3 lines are "written" and subsequently "read" by the following reactions:

Pitz, Robert W.↗

Assessment of the Interstellar Processes Leading to Deuterium Enrichment in Meteoritic Organics

The presence of isotopic anomalies is the most unequivocal demonstration that meteoritic material contains circumstellar or interstellar components. In the case of organic compounds in meteorites and interplanetary dust particles (IDPs), the most useful isotopic tracer has been deuterium (D). We discuss four processes that are expected to lead to D enrichment in interstellar materials and describe how their unique characteristics can be used to assess their relative importance for the organics in meteorites. These enrichment processes are low temperature gas phase ion-molecule reactions, low temperature gas-grain reactions, gas phase unimolecular photodissociation, and ultraviolet photolysis in D-enriched ice mantles. Each of these processes is expected to be associated with distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.), especially in the molecular population of polycyclic aromatic hydrocarbons (PAHs). We describe these differences and discuss how they may be used to delineate the various interstellar processes that may have contributed to meteoritic D enrichments. We also briefly discuss how these processes may affect the isotopic distributions in C, 0, and N in the same compounds.

Sandford, Scott A.↗

The Coupling of ClONO2, ClO, and NO2 in the Lower Stratosphere From in Situ Observations Using the NASA ER-2 Aircraft

The first in situ measurements of ClONO2 in the lower stratosphere, acquired using the NASA ER-2 aircraft during the Polar Ozone Loss in the Arctic Region in Summer (POLARIS) mission, are combined with simultaneous measurements of ClO, NO2, temperature, pressure, and the calculated photolysis rate coefficient (J(sub ClONO2)) to examine the balance between production and loss of ClONO2. The observations demonstrate the ClONO2 photochemical steady state measurement, [ClONO2](sup PSS) = k[ClO][No2]/J(sub ClONO2), is in good agreement with the direct measurement, [ClONO2](sup MEAS). For the bulk of the data (80%), where T > 220 K and latitudes > 45 N, [ClONO2](sup PPS) = 1.15 +/- 0.36(1-sigma)[ClONO2](sup MEAS), while for T< 220 K and latitudes < 45 N, the result is somewhat less at 1.01 +/- 0.30. The cause of the temperature and/or latitude trend is unidentified. These results are independent of solar zenith angle and air density, thus there is no evidence in support of a pressure-dependent quantum yield for photodissociation of ClONO2 at wavelengths > 300 nm. These measurements confirm the mechanism by which active nitrogen (NOx = NO + NO2) controls the abundance of active chlorine (Clx = ClO + Cl) in the stratosphere.

Stimpfle, R. E.↗

Excitation of the E2 and W1 "Arched" Filaments Near the Galactic Center as Deduced from Far-Infrared Spectroscopy

We present measurements of the far-infrared (FIR) fine structure lines [S III] (33 microns), [Si II] (35 microns), [O III] (51, 88 microns), [O I] (63 microns) and [C II] (158 microns) and the adjacent continua along a scan crossing the E2 and W1 thermal radio filaments in the Galactic center 'Arc'. The deduced electron density and excitation vary along the scan by less than factors of two and three, respectively. The properties of the two filaments are similar: the line and continuum fluxes peak at the radio ridge, and the ridge/off-ridge contrast is greatest for the FIR continuum and ionized lines, lower for the single dish radio measurements (Sofue et al. 1986), and smallest for the low excitation lines. The spatial coincidence of the FIR and radio peaks demonstrates that any excitation mechanism for the radio continuum filaments must also account for the FIR line and continuum emission. The FIR luminosity of approx. 3 x 10(exp 5) Solar Luminosity per beam, and the association of [O III] emission with the filaments poses difficulties for shock and MHD models. Photoionization of molecular cloud edges by a random distribution of stars is the most likely excitation mechanism among those proposed. The continuum and the low excitation line fluxes are consistent with an origin in photodissociated molecular material adjacent to the photoionized gas.

Colgan, Sean W.J.↗

The Nature of Ultraluminous Galaxies: Infrared Space Observatory Analysis and Instrument Team

The scientific goal of the proposed research was to investigate the physical conditions in the nuclear regions of infrared luminous galaxies by carrying out detailed infrared spectroscopic observations of a large sample of infrared luminous galaxies. During the past year, these observations have been successfully analyzed and extensive modeling using photoionization and photodissociation codes has been carried out. Two first-author publications and a second-author publication have been submitted to the Astrophysical Journal and results were presented at two invited talks. Four additional journal papers are in preparation and will be submitted during year 2 of the grant. The secondary project included in this program was the development of a near-infrared cryogenic Fabry-Perot interferometer for use on future large aperture telescopes. System integration and room temperature testing was successfully carried out for this project during year 1.

Satyapal, Shobita↗

Cooling of the Interstellar Medium

This talk will review the various heating and cooling processes in the interstellar medium. The most important heating processes include the photoelectric effect on dust grains and PAH molecules. Cooling of the gas in the interstellar medium is dominated by emission in the far infrared fine-structure lines of OI, CII, SiII, and CI, and the rotational transitions of CO. Which of these heating and cooling processes dominates in a given region depends on its physical and especially chemical conditions, which in turn depend themselves on the interstellar UV radiation field. As a result of the interplay of these processes, the interstellar medium is organized in various structures with distinctly different physical conditions (i.e., temperature, density, and degree of ionization). The dominant cooling lines of the neutral interstellar medium have been studied using the Kuiper Airborne Observatory, balloon-borne instruments, and recently space-based missions (IRTS, ISO). These observations have concentrated on dense regions illuminated by strong UV fields from nearby stars, so-called PhotoDissociation Regions (PDRs). These observations allow us to study in detail the interaction of UV photons observations allow us to study in detail the interaction of UV photons and the interstellar gas and dust. Detailed theoretical models have been developed for PDRs. These will be reviewed and compared to the observations. Recent space based missions have measured the dominant cooling line of the galaxy, the [CII] 158 micron line. These observations and their implications will be reviewed.

Tielens, A. G. G. M.↗

Infrared Observations of G0.18-0.04

The Galactic Center H(II) region, G0.18-0.04, the 'Sickle', is located where the nonthermal 'Arc' crosses the Galactic plane. The Sickle appears to be the ionized edge of a dense molecular cloud. The source of ionization has been ascribed to both the interaction of the cloud with the magnetic field of the Arc and to the hot stars in the adjacent cluster, AFGL 2004, also known as the 'Quintuplet Cluster'. This paper addresses the relative locations of the stars, the ionized and molecular gas, and the sources of gas excitation and dust heating. Using NASA's Kuiper Airborne Observatory, we have observed the far infrared forbidden lines of [S(III)] 18.7 and 33.5 micrometers, [Si(II)] 34.8 micrometers, [Ne(III)] 36.0 micrometers, [O(III)] 51.8 and 88.4 micrometers, [N(III)] 57.3 micrometers, [O(II)] 63.2 and 146 micrometers, [C(II)] 158 micrometers, and [N(II)] 205 micrometers and the adjacent continua at 11 positions around G0.18-0.04, including G0.15-0.05, the 'Pistol', in a beamsize of 40 - 60 arcsec. The electron density, the ionic abundances, and the ionization structure of the H(II) region are estimated from the doubly ionized line fluxes. The density and radiation field found in the photodissociation region (PDR) between the H(II) region and the molecular cloud are estimated from the [C(II)] and [O(I)] line fluxes and the far-infrared continuum. We compare the ionization structure and the PDR properties to shell models of H(II) regions with varying distances from their exciting stars. The agreement of observations and models indicates that the hot stars of AFGL 2004 are the likely source of ionization of the Sickle. Additional hot stars are necessary to ionize the more outlying positions. However, because of its low ionization and high PDR radiation field, the Pistol cannot be as close to AFGL 2004 as indicated by its close proximity on the sky. Instead, the Pistol is probably ionized by the luminous blue variable candidate, Pistol Source A. We estimated the extinction to the region from the distribution of the J, H, and K' magnitudes of the stars in the field that we measured from the Anglo-Australian telescope and from the IRAS LRS spectrum of AFGL 2004. The extinction is fairly uniform, with no enhancement from the molecular cloud. The strength of Brackett gamma, the 19-micrometer lines and continuum, and the IRAS 25-micrometer continuum are all consistent with the absence of a dense, foreground molecular cloud. We conclude that the H(II) region is on the near side of the dense cloud.

Simpson, Janet P.↗

Interstellar Processes Leading to Molecular Deuterium Enrichment and Their Detection

Large deuterium (D) enrichments in meteoritic materials indicate that interstellar organic materials survived incorporation into parent bodies within the forming Solar System. These enrichments are likelier due to one or more of four distinct astrochemical processes. These are (1) low temperature gas phase ion-molecule reactions; (2) low temperature gas-grain reactions; (3) gas phase unimolecular photodissociation, and (4) ultraviolet photolysis in D-enriched ice mantles. Each of these processes should be associated with molecular carriers having, distinct regiochemical signatures (D placement on the product molecules, correlation with specific chemical functionalities, etc.). These processes are reviewed and specific spectroscopic signatures for the detection of these processes in space are identified and described.

Sandford, Scott A.↗

Destruction of Interstellar Dust

Interstellar dust is an important component of the interstellar medium. Dust grains are the dominant opacity source and thus regulate the radiative transfer in the interstellar medium. Besides the spectral characteristics of sources, dust therefore influences directly the molecular composition of clouds through photodissociation and the heating of the gas through the photoelectric effect. Furthermore, dust grains also provide surfaces for active chemistry. This paper will review the destruction of interstellar dust with an emphasis on processing by interstellar shocks. Interstellar dust is affected by a variety of processes. Stars in the late stages of their evolution form dust grains by chemical nucleation and growth and injected them into the ISM. Grains in the ISM are processed by strong shock waves which sputter, vaporize, diamondize, and shatter them. The physics of interstellar shock waves and of these destruction processes will be reviewed. The ISM is organized in a number of phases: HI and molecular clouds, warm (neutral/ionized) intercloud medium, and coroner gas. Dust destruction is dominated by supernova shock waves in the intercloud medium. Because of rapid exchange of dust and gas between the phases, the effects of this are felt through all phases. This will be briefly discussed.

Tielens, A. G. G. M.↗