Vacuum-ultraviolet photochemistry. IV - Primary processes in the photolysis of water at 1470 angstrom units.
Photolysis of water at 1470 angstroms in absence and presence of ethylene
DEUTERIUM↗
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Vacuum-ultraviolet photochemistry. IX - Primary and chain processes in the photolysis of hydrogen peroxide
Atomic and molecular hydrogen formation in photolysis of hydrogen peroxide
HYDROGEN PEROXIDE↗
Vacuum-ultraviolet photochemistry. X - Primary processes in the photolysis of methylacetylene at 1470 and 1236 angstrom
Molecular elimination of hydrogen during methyl acetylene photolysis in vacuum ultraviolet
HYDROGEN ATOM↗
Vacuum-ultraviolet photochemistry. IX - Primary and chain processes in the photolysis of hydrogen peroxide.
Primary processes leading to atomic and molecular hydrogen formation in hydrogen peroxide photolysis at 1236 A, noting OH formation
Decarlo, V. J.↗
The ultraviolet photochemistry of diacetylene - Direct detection of primary products of the metastable C4H2* + C4H2 reaction
The products of diacetylene's ultraviolet photochemistry over the 245-220 nm region were directly determined in experiments where C4H2 was excited within a small reaction tube attached to a pulsed nozzle. The products formed in the collisions of C4H2* with C4H2 were subsequently ionized by vacuum UV radiation (at 118 nm) in the ion source of a time-of-flight mass spectrometer. It was found that the reaction of C4H2* with C4H2 produces C6H2 (+C2H2), C8H2 (+2H,H2), and C8H3 (+H), confirming the results of Glicker and Okabe (1987). Under certain conditions, secondary products were observed. Mechanisms for the observed reactions are proposed.
Bandy, Ralph E.↗
The Effects of Consistent Chemical Kinetics Calculations on the Pressure-Temperature Profiles and Emission Spectra of Hot Jupiters
In this work we investigate the impact of calculating non-equilibrium chemical abundances consistently with the temperature structure for the atmospheres of highly-irradiated, close-in gas giant exoplanets. Chemical kinetics models have been widely used in the literature to investigate the chemical compositions of hot Jupiter atmospheres which are expected to be driven away from chemical equilibrium via processes such as vertical mixing and photochemistry. All of these models have so far used pressure-temperature (P-T) profiles as fixed model input. This results in a decoupling of the chemistry from the radiative and thermal properties of the atmosphere, despite the fact that in nature they are intricately linked. We use a one-dimensional radiative-convective equilibrium model, ATMO, which includes a sophisticated chemistry scheme to calculate P-T profiles which are fully consistent with non-equilibrium chemical abundances, including vertical mixing and photochemistry. Our primary conclusion is that, in cases of strong chemical disequilibrium, consistent calculations can lead to differences in the P-T profile of up to 100 K compared to the P-T profile derived assuming chemical equilibrium. This temperature change can, in turn, have important consequences for the chemical abundances themselves as well as for the simulated emission spectra. In particular, we find that performing the chemical kinetics calculation consistently can reduce the overall impact of non-equilibrium chemistry on the observable emission spectrum of hot Jupiters. Simulated observations derived from non-consistent models could thus yield the wrong interpretation. We show that this behaviour is due to the non-consistent models violating the energy budget balance of the atmosphere.
planets and satellites↗
Direct detection of C4H2 photochemical products - Possible routes to complex hydrocarbons in planetary atmospheres
The photochemistry of diacetylene (C4H2), the largest hydrocarbon to be unambiguously identified in planetary atmospheres, is of considerable importance to understanding the mechanisms by which complex molecules are formed in the solar system. In this work, the primary products of C4H2's ultraviolet photochemistry were determined in a two-laser pump-probe scheme in which the products of C4H2 photoexcitation are detected by vacuum ultraviolet photoionization in a time-of-flight mass spectrometer. Three larger hydrocarbon primary products were observed with good yield in the C4H2 + C4H2 reaction: C6H2, C8H2, and C8H3. Neither C6H2 or C8H3 is anticipated by current photochemical models of the atmospheres of Titan, Uranus, Neptune, Pluto, and Triton. The free hydrogen atoms that are released during the formation of the C8H3 and C8H2 products also may partially offset the role of C4H2 in catalyzing the recombination of free hydrogen atoms in the planetary atmospheres.
Bandy, Ralph E.↗
The vertical distribution and origin of HCN in Neptune's atmosphere
Measurements and modeling of the (3-2) rotational line of hydrogen cyanide at 265.9 GHz in Neptune's atmosphere are presented. High signal-to-noise observations provide information on the HCN vertical distribution in Neptune's stratosphere. The HCN mixing ratio is found to be nearly uniform with height above the condensation level. Best fits occur for HCN distributions that have a slight increase with altitude. A least-squares analysis yields a mixing ratio of (3.2 +/- 0.8)10(exp -10) at 2 mbar and a mean mixing ratio scale height of 250(sup 750)(sub -110) km in the 0.1-3 mbar region. To interpret these results, we developed a photochemical model of HCN. HCN formation is initiated by the reaction between CH3 radicals, produced from methane photochemistry, and N atoms. The primary sink for HCN is condensation, with minor contributions from photolysis and chemical losses. Two possible sources of N atoms are investigated: (1) infall of N escaped from Triton's upper atmosphere, and (2) galactic cosmic ray (GCR) impact on internal N2. Given the uncertainties on (i) the transport and possible ionization of N in Neptune's magnetosphere, and the fate of N(+) reaching Neptune's upper atmosphere and (ii) the N2 mixing ratio in Neptune's deep atmosphere, we suggest that both sources of N atoms may significantly contibute to the formation of HCN.
Lellouch, Emmanuel↗
Photochemical Studies of Chemistry in the Outer Solar System
The goal of the proposed science investigation is to gain a quantitative understanding of chemical processes and their coupling with atmospheric dynamics in the reducing atmospheres of the outer solar system, with a particular focus on Infrared Space Observatory (ISO) observations and future experiments such as the Cassini Mission to Saturn and Titan. The proposed work is divided into two related tasks. We have carried out a systematic comparison between atmospheric models for every giant planet and Titan, which employ a consistent set of photochemical reactions. Combined with recent observations of hydrocarbon species by ISO, this can provide the most rigorous test of our current understanding of the photochemistry of hydrocarbon in the outer solar system. The emphasis will be on the methyl radical (CH3), first detected by IS0 in the atmospheres of Saturn and Neptune (Bezard et al. 1998). CH3 is one of the most important radicals in the hydrocarbon photochemistry because it is the primary product of methane photolysis and plays an essential role in forming C2H6, the most abundant and stable C2 species. A fundamental understanding of the distribution of CH3 provides unique insights into the chemistry of hydrocarbons as well as comparative planetology.
Yung, Yuk L.↗
Understanding the Atmosphere of 51 Eri b: Do Photochemical Hazes Cloud the Planets Spectrum?
The first young giant planet to be discovered by the Gemini Planet Imager was the (is) approximately 2MJ planet 51 Eri b. This approximately 20 Myr old young Jupiter is the first directly imaged planet to show unmistakable methane in H band. To constrain the planet's mass, atmospheric temperature, and composition, the GPI J and H band spectra as well as some limited photometric points were compared to the predictions of substellar atmosphere models. The best fitting models reported in the discovery paper (Macintosh et al. 2015) relied upon a combination of clear and cloudy atmospheric columns to reproduce the data. However for an object as cool as 700 K, the origin of the cloud coverage is somewhat puzzling, as the global silicate and iron clouds would be expected to have sunk well below the photosphere by this effective temperature. While strong vertical mixing in these low gravity atmospheres remains a plausible explanation, we have explored whether atmospheric photochemistry, driven by the UV flux from the primary star, may yield hazes that also influence the observed spectrum of the planet. To explore this possibility we have modeled the atmospheric photochemistry of 51 Eri b using two state-of-the-art photochemical models, both capable of predicting yields of complex hydrocarbons under various atmospheric conditions. In our presentation we will summarize the modeling approach employed to characterize 51 Eri b, explaining constraints on the planet's effective temperature, gravity, and atmospheric composition and also present results of our studies of atmospheric photochemistry. We will discuss whether photochemical hazes could indeed be responsible for the particulate opacity that apparently sculpts the spectrum of the planet.
GPI - Gemini Planet Imager↗
Modeling and Data Analysis of SONEX Observations
Primary focus of the study is on the sources, photochemistry and transport of reactive nitrogen species, O3, as well as other O3 precursors such as NMHC and CO. Major objectives are: (1) Identify the major sources of NO(x) and quantify the contribution of each source to the NO(x) distribution in the free troposphere, particularly in the upper troposphere. (2) Understand the odd hydrogen photochemistry and the recycling of NO(x) in the free troposphere. (3) Evaluate the photochemical production and destruction of O3. A combination of modeling and data analysis/interpretation approach is used. We use a three-dimensional model and a box model to simulate, analyze, and interpret the observations. Both models are needed because they are complementary and each has its advantages and limitations. Proven analytical techniques, including correlation of NOx with various tracers and with different air masses, are applied to both observations and model results to deduce useful information toward accomplishing the objectives. In addition, the SONEX observations are compared and analyzed in a systematic way against other airborne experiments conducted over remote atmosphere, especially those from NASA GTE experiments, AASE 1 and 2, and SUCCESS.
Liu, Shaw C.↗
Photochemistry of acetylene at 1470 A
The considered study was conducted to assess the importance of the major primary photochemical process of acetylene at 1470 A, to clarify the role of the metastable excited state, and to obtain information on the rates of C2H reactions with H2 and CH4. Concerning the photodissociation process of acetylene, it was found that at acetylene pressures below 0.8 Torr the direct dissociation process (C2H2 yields C2H + H) is the most important primary photochemical process with a quantum yield of 0.3. Another primary process may be the production of H2 with a quantum yield of approximately 0.1 (C2H2 yields C2 + H2). At acetylene pressures above 0.8 Torr diacetylene is formed by the direct dissociation process followed by the reaction: C2H + C2H2 yields C4H2 + H. At pressures above 20 Torr benzene becomes an important product with a concomitant decrease of diacetylene. The role of acetylene in the photochemistry of the Jovian atmosphere is also considered
Okabe, H.↗
Photochemistry chemical kinetics in the interstellar medium.
Gas phase processes involving interstellar molecules are considered. The primary process is photodissociation in the ambient radiation field. In obscured regions, a combination of Johnson's (1965) and Stecher's (1969) Perseus extinction curves was used to obtain the radiation field as a function of the extinction at 5,500 A. On the basis of laboratory measurements, it is concluded that the molecules of water, ammonia, methane, and formaldehyde have lifetimes less than one hundred years.
Donn, B.↗
Vertical distributions of molecular hydrogen off the eastern and Gulf coasts of the United States
The vertical distributions of molecular hydrogen (H2) and carbon monoxide (CO) were determined during spiraling maneuvers from aircraft off the eastern coast of the United States and over the Gulf of Mexico. H2 was always at its lowest levels in the boundary layer, averaging about 500 parts per billion by volume (ppbv). H2 mixing ratios determined in the free troposphere were typically higher (600-700 ppbv), and often suggested a small progressive increase with altitude. Several large free-tropospheric H2 plumes (mixing ratios as high as 1-2 parts per million by volume) were implied by the data. These H2 plumes were not always accompanied by corresponding increases in CO mixing ratios. This result is most difficult to explain when it is noted that the primary atmospheric sources for molecular H2 are considered to be combustion and photochemistry, both of which should be strong CO sources also.
Cofer, Wesley R., III↗
Laboratory observations of the photochemistry of parent molecules: A review
The photochemistry of possible parent molecules of comets has been reviewed. Quantum yields for many of the primary processes are unknown. Energy partitioning among the fragments has not been extensively investigated. A few of the studies have been performed as a function of the number of collisions that the excited molecules undergo, so that possible differences that may occur in a cometary environment may be ascertained.
Jackson, W. M.↗
Photochemistry and lifetimes of interstellar molecules.
Quantitative discussion of the photochemistry and lifetime against photodecomposition of five interstellar molecules: H2CO, NH3, H2O, CH4, and CO. For the first four molecules, primary photochemical decomposition processes yielding atomic and molecular hydrogen are considered in addition to photoionization. The quantum yield for decomposition of these molecules is unity. For CO, only decomposition to ground-state carbon and oxygen atoms occur, but the quantum yield is not known and may be considerably less than unity. The radiation field in obscuring clouds is estimated, using an interstellar extinction curve for the Perseus region.
Stief, L. J.↗
Acetone in theGlobal Troposphere: Its Possible Role as a Global Source of PAN
Oxygenated hydrocarbons are thought to be important components of the atmosphere but, with the exception of formaldehyde, very little about their distribution and fate is known. Aircraft measurements of acetone (CH3COCH3), PAN (CH3CO3NO2) and other organic species (e. g. acetaldehyde, methanol and ethanol) have been performed over the Pacific, the southern Atlantic, and the subarctic atmospheres. Sampled areas extended from 0 to 12 km altitude over latitudes of 70 deg N to 40 deg S. All measurements are based on real time in-situ analysis of cryogenically preconcentrated air samples. Substantial concentrations of these oxygenated species (10-2000 ppt) have been observed at all altitudes and geographical locations in the troposphere. Important sources include, emissions from biomass burning, plant and vegetation, secondary oxidation of primary non-methane hydrocarbons, and man-made emissions. Direct measurements within smoke plumes have been used to estimate the biomass burning source. Photochemistry studies are used to suggest that acetone could provide a major source of peroxyacetyl radicals in the atmosphere and play an important role in sequestering reactive nitrogen. Model calculations show that acetone photolysis contributes significantly to PAN formation in the middle and upper troposphere.
Singh, H. B.↗
Making Sense of Plant Health
Ciencia, Inc. created a new device, known as a Portable Photosynthesis Analyzer, or Phase Fluorometer, that provides real-time data about the photochemical efficiency of phytoplankton and other plant forms. The commercial version of this technology is used for photosynthesis research and offers major benefits to the field of life science. This new instrument is the first portable instrument of its kind. Through a license agreement with Ciencia, Oriel Instruments, of Stratford, Connecticut, manufactures and markets the commercial version of the instrument under the name LifeSense.TMLifeSense is a 70 MHz single-frequency fluorometer that offers unrivaled capabilities for fluorescence lifetime sensing and analysis. LifeSense provides information about all varieties of photosynthetic systems. Photosynthesis research contributes important health assessments about the plant, be it phytoplankton or a higher form of plant life. With its unique sensing capabilities, LifeSense furnishes data regarding the yield of a plant's photochemistry, as well as its levels of photosynthetic activity. The user can then gain an extremely accurate estimate of the plant's chlorophyll biomass, primary production rates, and a general overview of the plant's physiological condition.
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