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All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Self-deactivation of water vapor - Role of the dimer

A phenomenological multiple-relaxation theory of the deactivation rate constant for the nu-2 (1 - 0) bending mode of water vapor is presented which incorporates the role not only of the excited monomer but also of the bound molecular complex, in particular the dimer. The deactivation takes place by means of three parallel processes: (1) collisional deexcitation of the excited monomer, (2) a two-step reaction involving association and spontaneous redissociation of an H2O collision complex, and (3) spontaneous dissociation of the stably bound H2O dimer. Oxygen, but not nitrogen or argon, serves as an effective chaperon for the formation of the activated complex. This observation explains the impurity dependence of the self-deactivation rate constant of water vapor. Analysis of an ultrasonic absorption peak based on the third process yields values for the standard entropy and enthalpy of dissociation of the stably bound H2O dimer.

Zuckerwar, A. J.↗
NASA NTRS2011

Initiating Molecular Growth in the Interstellar Medium via Dimeric Complexes of Observed Ions and Molecules

A feasible initiation step for particle growth in the interstellar medium (ISM) is simulated by means of ab quantum chemistry methods. The systems studied are dimer ions formed by pairing nitrogen containing small molecules known to exist in the ISM with ions of unsaturated hydrocarbons or vice versa. Complexation energies, structures of ensuing complexes and electronic excitation spectra of the encounter complexes are estimated using various quantum chemistry methods. Moller-Plesset perturbation theory (MP2, Z-averaged perturbation theory (ZAP2), coupled cluster singles and doubles with perturbative triples corrections (CCSD(T)), and density functional theory (DFT) methods (B3LYP) were employed along with the correlation consistent cc-pVTZ and aug-cc-pVTZ basis sets. Two types of complexes are predicted. One type of complex has electrostatic binding with moderate (7-20 kcal per mol) binding energies, that are nonetheless significantly stronger than typical van der Waals interactions between molecules of this size. The other type of complex develops strong covalent bonds between the fragments. Cyclic isomers of the nitrogen containing complexes are produced very easily by ion-molecule reactions. Some of these complexes show intense ultraviolet visible spectra for electronic transitions with large oscillator strengths at the B3LYP, omegaB97, and equations of motion coupled cluster (EOM-CCSD) levels. The open shell nitrogen containing carbonaceous complexes especially exhibit a large oscillator strength electronic transition in the visible region of the electromagnetic spectrum.

Bera, Partha P.↗
NASA NTRS1999

Proton-bound cluster ions in ion mobility spectrometry

Gaseous oxygen and nitrogen bases, both singly and as binary mixtures, have been introduced into ion mobility spectrometers to study the appearance of protonated molecules, and proton-bound dimers and trimers. At ambient temperature it was possible to simultaneously observe, following the introduction of molecule A, comparable intensities of peaks ascribable to the reactant ion (H2O)nH+, the protonated molecule AH+ and AH+ H2O, and the symmetrical proton bound dimer A2H+. Mass spectral identification confirmed the identifications and also showed that the majority of the protonated molecules were hydrated and that the proton-bound dimers were hydrated to a much lesser extent. No significant peaks ascribable to proton-bound trimers were obtained no matter how high the sample concentration. Binary mixtures containing molecules A and B, in some cases gave not only the peaks unique to the individual compounds but also peaks due to asymmetrical proton bound dimers AHB+. Such ions were always present in the spectra of mixtures of oxygen bases but were not observed for several mixtures of oxygen and nitrogen bases. The dimers, which were not observable, notable for their low hydrogen bond strengths, must have decomposed in their passage from the ion source to the detector, i.e. in a time less than approximately 5 ms. When the temperature was lowered to -20 degrees C, trimers, both homogeneous and mixed, were observed with mixtures of alcohols. The importance of hydrogen bond energy, and hence operating temperature, in determining the degree of solvation of the ions that will be observed in an ion mobility spectrometer is stressed. The possibility is discussed that a displacement reaction involving ambient water plays a role in the dissociation.

Non-NASA Center↗
NASA NTRS2002

Submillimeter Spectra of Low Temperature Gases and Mixtures

Submillimeter absorption spectra of nitrogen, nitrogen-argon mixtures, and methane have been measured using temperatures and pressures near to those found in the atmospheres of Titan and Saturn. The experiments show the spectral signature of dimers which will likely appear in far-infrared spectra of Titan that will be obtained by the Composite Infrared Spectrometer (CIS) onboard the Cassini spacecraft. The recent CIRS spectrum of Jupiter shows far-infrared spectral lines of methane and the corresponding lines are observed in the laboratory. We are extending this work to lower frequencies using a new differential Michelson interferometer that operates over the frequency region 3-30 1/cm..

Wishnow, E. H.↗
NASA NTRS1977

Nitrogen-induced absorption of oxygen in the Herzberg continuum

Total absorption of O2 induced by collisions with N2 has been measured at room temperature in the Hersberg continuum using a one meter normal incidence grating monochromator. The enhanced absorption is ascribed to the formation of O2-O2 and O2-N2 dimers. The interaction constants for these dimers are determined and utilized to investigate their effect on the absorption of solar radiation in the stratosphere.

Shardanand, MR.↗
NASA NTRS1989

Stratospheric ozone - Impact of human activity

The current knowledge of the chemistry of the stratosphere is reviewed, with particular consideration given to the measurements from the Atmospheric Trace Molecule Spectroscopy (ATMOS) experiment and from the Airborne Antarctic Ozone Experiment. Analysis of the ATMOS data at 30 deg N suggests that the current understanding of the contemporary-stratosphere chemistry at mid-latitudes is relatively complete, except for possible problems with the diurnal variations of N2O5 at low altitudes, and with ClNO3 at higher altitudes. Except for some difficulties with these two compounds, the data from ATMOS agree well with the gas phase models for nitrogen and chlorine species at 30 deg N in spring. It is emphasized that, in addition to the HOCl mechanism proposed by Solomon et al. (1986), the ClO-BrO scheme proposed by McElroy et al. (1986), and the ClO dimer mechanism introduced by Molina and Molina (1987), other processes exist that are responsible for ozone removal.

Mcelroy, Michael B.↗
NASA NTRS2018

A Cloud Algorithm Based on the O2-O2 477 nm Absorption Band Featuring an Advanced Spectral Fitting Method and the Use of Surface Geometry-Dependent Lambertian-Equivalent Reflectivity

We discuss a new cloud algorithm that retrieves an effective cloud pressure, also known as cloud optical centroid pressure (OCP), from oxygen dimer (O2-O2) absorption at 477nm after determining an effective cloud fraction (ECF) at 466nm, a wavelength not significantly affected by trace-gas absorption and rotational Raman scattering. The retrieved cloud products are intended for use as inputs to the operational nitrogen dioxide (NO2) retrieval algorithm for the Ozone Monitoring Instrument (OMI) flying on the Aura satellite. The cloud algorithm uses temperature-dependent O2-O2 cross sections and incorporates flexible spectral fitting techniques that account for specifics of the surface reflectivity. The fitting procedure derives O2-O2 slant column densities (SCDs) from radiances after O3, NO2, and H2O absorption features have been removed based on estimates of the amounts of these species from independent OMI algorithms. The cloud algorithm is based on the frequently used mixed Lambertian-equivalent reflectivity (MLER) concept. A geometry-dependent Lambertian-equivalent reflectivity (GLER), which is a proxy of surface bidirectional reflectance, is used for the ground reflectivity in our implementation of the MLER approach. The OCP is derived from a match of the measured O2-O2 SCD to that calculated with the MLER method. Temperature profiles needed for computation of vertical column densities are taken from the Global Modeling Initiative (GMI) model. We investigate the effect of using GLER instead of climatological LER on the retrieved ECF and OCP. For evaluation purposes, the retrieved ECFs and OCPs are compared with those from the operational OMI cloud product, which is also based on the same O2-O2 absorption band. Impacts of the application of the newly developed cloud algorithm to the OMI NO2 retrieval are discussed.

cloud fraction and pressure↗
NASA NTRS1978

Temperature effect on nitrogen-induced absorption of oxygen in the Herzberg continuum

The effect of temperature on the total absorption of O2 induced by collisions with N2 has been measured at various temperatures in the Herzberg continuum using a one-meter normal-incidence grating monochromator. It is observed that absorption increases as the temperature decreases, which is ascribed to changes in the rate of formation of the dimers O2-O2 and O2-N2. The interaction constants for these dimers are determined as functions of temperature and then utilized to calculate the heats of dissociation of O2-O2 and O2-N2. Their respective values are found to be 0.0146 + or - 0.001 and 0.425 + or - 0.002 eV. Also, the interaction constants for these dimers measured at 200 + or - 1 K are utilized to investigate their effect on the absorption of solar radiation in the stratosphere.

Shardanand, MR.↗
NASA NTRS1990

Calculations of ozone destruction during the 1988/89 Arctic winter

Calculations of ozone depletion during the 1988/89 Arctic winter using a Lagrangian coupled photochemical-microphysical model are presented. Abundances of ClO in excess of 1 ppbv were observed at the end of the Airborne Arctic Stratospheric Expedition on February 10, 1989. These are shown to be consistent with the removal of more than 90 percent of the reactive nitrogen and the conversion of more than 80 percent of reservoir chlorine to active forms. This chemical state implies that ozone losses of more than 20 ppbv/day can be sustained in heavily denitrified air throughout much of February according to current photochemistry. As much as 74 percent of the loss is calculated to be due to ClO dimer photolysis. Following the warming of the vortex in mid-February 1989, ozone loss through ClO dimer photolysis becomes less effective as the rate of thermal decomposition of the ClO dimer increases. Thus, model results suggest that thermal decomposition of the dimer plays an important role in limiting ozone loss in the Arctic spring.

Mckenna, D. S.↗
NASA NTRS2011

Exploring the Fate of Nitrogen Heterocycles in Complex Prebiotic Mixtures

A long standing question in the field of prebiotic chemistry is the origin of the genetic macromolecules DNA and RNA. DNA and RNA have very complex structures with repeating subunits of nucleotides, which are composed of nucleobases (nitrogen heterocycles) connected to sugar-phosphate. Due to the instability of some nucleobases (e.g. cytosine), difficulty of synthesis and instability of D-ribose, and the likely scarcity of polyphosphates necessary for the modern nucleotides, alternative nucleotides have been proposed for constructing the first genetic material. Thus, we have begun to investigate the chemistry of nitrogen heterocycles in plausible, complex prebiotic mixtures in an effort to identify robust reactions and potential alternative nucleotides. We have taken a complex prebiotic mixture produced by a spark discharge acting on a gas mixture of N2, CO2, CH4, and H2, and reacted it with four nitrogen heterocycles: uracil, 5-hydroxymethyluracil, guanine, and isoxanthopterin (2-amino-4,7-dihydroxypteridine). The products of the reaction between the spark mixture and each nitrogen heterocycle were characterized by liquid chromatography coupled to UV spectroscopy and Orbitrap mass spectrometry. We found that the reaction between the spark mixtUl'e and isoxanthopterin formed one major product, which was a cyanide adduct. 5-hydroxymethyluracil also reacted with the spark mixture to form a cyanide adduct, uracil-5-acetonitrile, which has been synthesized previously by reacting HCN with S-hydroxymethyluracil. Unlike isoxanthopterin, the chromatogram of the 5-hydroxymethyluracil reaction was much more complex with multiple products including spark-modified dimers. Additionally, we observed that HMU readily self-polymerizes in solution to a variety of oligomers consistent with those suggested by Cleaves. Guanine and uracil, the biological nucleobases, did not react with the spark mixture, even at high temperature (100 C). This suggests that there are alternative nucleobases which are more reactive under prebiotic conditions and may have been involved in producing precursor nucleotides.

Smith, Karen E.↗
NASA NTRS1994

Archean geochemistry of formaldehyde and cyanide and the oligomerization of cyanohydrin

The sources and speciation of reduced carbon and nitrogen inferred for the early Archean are reviewed in terms of current observations and models, and known chemical reactions. Within this framework hydrogen cyanide and cyanide ion in significant concentration would have been eliminated by reaction with excess formaldehyde to form cyanohydrin (glycolonitrile), and with ferrous ion to formferrocyanide. Natural reactions of these molecules would under such conditions deserve special consideration in modeling of primordial organochemical processes. As a step in this direction, transformation reactions have been investigated involving glycolonitrile in the presence of water. We find that glycolonitrile, formed from formaldehyde and hydrogen cyanide or cyanide ion, spontaneously cyclodimerizes to 4-amino-2-hydroxymethyloxazole. The crystalline dimer is the major product at low temperatue (approximately 0 C); the yield diminishes with increasing temperature at the expense of polymerization and hydrolysis products. Hydrolysis of glycolamide and of oxazole yields a number of simpler organic molecules, including ammonia and glycolamide. The spontaneous polymerization of glycolonitrile and its dimer gives rise to soluble, cationic oligomers of as yet unknown structure, and, unless arrested, to a viscous liquid, insoluble in water. A loss of cyanide by reaction with formaldehyde, inferred for the early terrestrial hydrosphere and cryosphere would present a dilemma for hypotheses invoking cyanide and related compounds as concentrated reactants capable of forming biomolecular precursor species. Attempts to escape from its horns may take advantage of the efficient concentration and separation of cyanide as solid ferriferrocyanide, and most directly of reactions of glycolonitrile and its derivatives.

Arrhenius, T.↗
NASA NTRS1993

Airborne Arctic Stratospheric Expedition 2: An overview

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), stages from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromide radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O. In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-1), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NO(x) and to some degree NO(y) were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, ClO was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of ClO and its dimer ClOOCl. This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-2): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30 deg N in the winter/spring northern hemisphere reported in satellite observations?

Anderson, James G.↗
NASA NTRS1993

Airborne Arctic Stratospheric Expedition 2: An Overview

The sudden onset of ozone depletion in the antarctic vortex set a precedent for both the time scale and the severity of global change. The Airborne Antarctic Ozone Experiment (AAOE), staged from Punta Arenas, Chile, in 1987, established that CFCs, halons, and methyl bromide, the dominant sources of chlorine and bromine radicals in the stratosphere, control the rate of ozone destruction over the Antarctic; that the vortex is depleted in reactive nitrogen and water vapor; and that diabatic cooling during the antarctic winter leads to subsidence within the vortex core, importing air from higher altitudes and lower latitudes. This last conclusion is based on observed dramatic distortion in the tracer fields, most notably N2O. In 1989, the first Airborne Arctic Stratospheric Expedition (AASE-I), staged from Stavanger, Norway, and using the same aircraft employed for AAOE (the NASA ER-2 and the NASA DC-8), discovered that while NO(x) and to some degree NO(y) were perturbed within the arctic vortex, there was little evidence for desiccation. Under these (in contrast to the antarctic) marginally perturbed conditions, however, Cl0 was found to be dramatically enhanced such that a large fraction of the available (inorganic) chlorine resided in the form of Cl0 and its dimer ClOOCl. This leaves two abiding issues for the northern hemisphere and the mission of the second Airborne Arctic Stratospheric Expedition (AASE-II): (1) Will significant ozone erosion occur within the arctic vortex in the next ten years as chlorine loading in the stratosphere exceeds four parts per billion by volume? and (2) Which mechanisms are responsible for the observed ozone erosion poleward of 30 deg N in the winter/spring northern hemisphere reported in satellite observations?

Anderson, James G.↗