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The atomic carbon emission C I line feature at 1657 Å (^(3)P^(0)_(J) -^(3)P_J ) in the upper atmosphere of Titan is first identified from the airglow spectra obtained by the Cassini Ultra-violet Imaging Spectrograph. A one-dimensional photochemical model of Titan is used to study the photochemistry of atomic carbon on Titan. Reaction between CH and atomic hydrogen is the major source of atomic carbon, and reactions with hydrocarbons (C_2H_2 and C_2H_4) are the most important loss processes. Resonance scattering of sunlight by atomic carbon is the dominant emission mechanism. The emission intensity calculations based on model results show good agreement with the observations.

The reaction of the dicarbon molecule (C2) in its ^(1)Σ_(g) + electronic ground state with hydrogen cyanide HCN(X^(1)Σ^+) is investigated in a crossed molecular beam setup to untangle the formation of the cyanoethynyl radical CCCN(X^(2)Σ^+) in hydrocarbon-rich atmospheres of planets and their moons such as Titan. Combined with electronic structure and rate theory calculations, we show that this elementary reaction is rapid, has no entrance barriers, and yields CCCN via successive rearrangements of the initial HC_(3)N collision complex to the cyanoacetylene intermediate (HCCCN) followed by unimolecular decomposition of the latter without exit barrier. New photochemical models imply that this radical could serve as a key building block to form more complex molecules as observed in situ by the Cassini spacecraft, ultimately leading to organic aerosol particles, which make up the orange-brownish haze layers in Titan's atmosphere.

Tables that have been used as a reference for nearly 50 years for the intensity and polarization of reflected and transmitted light in Rayleigh scattering atmospheres have been found to be inaccurate, even to four decimal places. We convert the integral equations describing the X and Y functions into a pair of coupled integrodifferential equations that can be efficiently solved numerically. Special care has been taken in evaluating Cauchy principal value integrals and their derivatives that appear in the solution of the Rayleigh scattering problem. The new approach gives results accurate to eight decimal places for the entire range of tabulation (optical thicknesses 0.02–1.0, surface reflectances 0–0.8, solar and viewing zenith angles 0 ◦ –88.85 ◦ , and relative azimuth angles 0 ◦ –180 ◦ ), including the most difficult case of direct transmission in the direction of the sun. Revised tables have been created and stored electronically for easy reference by the planetary science and astrophysics community.

We investigated the formation of two C3H2O isomers, i.e., cyclopropenone (c-C3H2O) and propynal (HCCCHO), inbinaryicemixturesof carbonmonoxide(CO)andacetylene(C2H2)at10Kinanultrahighvacuummachineonhighenergy electron irradiation. The chemical evolution of the ice samples was followed online and in situ via a Fourier transform infraredspectrometerand a quadrupolemassspectrometer. The temporalprofilesof the cyclopropenoneand propynal isomers suggest (pseudo-) first-order kinetics. The cyclic structure (c-C3H2O) is formed via an addition of triplet carbon monoxide to ground-state acetylene (or vice versa); propynal (HCCCHO) can be synthesized from a carbonmonoxideYacetylenecomplexviaa[HCO ... CCH] radical pairinsidethematrixcage.Theselaboratorystudies showedforthefirsttimethatbothC3H2Oisomerscanbeformedinlow-temperatureicesvianonequilibriumchemistry initiated by energetic electrons as formed in the track of Galactic cosmic ray particles penetrating interstellar icy grains in cold molecular clouds. Our results can explain the hitherto unresolved gas phase abundances of cyclopropenone in star-formingregions via sublimation of c-C3H2O as formed on icy grains in the cold molecularcloud stage. Implications for the heterogeneous oxygen chemistry of Titan and icy terrestrial planets and satellites suggest that the production of oxygen-bearing molecules such as C3H2O may dominate on aerosol particles compared to pure gas phase chemistry. Subject headingg astrobiology — astrochemistry — ISM: molecules — planets and satellites: individual (Titan) Online material: color figures

Cross sections for photoabsorption of NH_3, NH_2D, NHD_2, and ND_3 in the spectral region 140-220 nm were determined at ~298 K using synchrotron radiation. Absorption spectra of NH_2D and NHD_2 were deduced from spectra of mixtures of NH_3 and ND_3, of which the equilibrium concentrations for all four isotopologues obey statistical distributions. Cross sections of NH_2D, NHD_2, and ND_3 are new. Oscillator strengths, an integration of absorption cross sections over the spectral lines, for both A ← X and B ← X systems of NH_3 agree satisfactorily with previous reports; values for NH_2D, NHD_2, and ND_3 agree with quantum chemical predictions. The photolysis of NH_3 provides a major source of reactive hydrogen in the lower stratosphere and upper troposphere of giant planets such as Jupiter. Incorporating the measured photoabsorption cross sections of NH_3 and NH_2D into the Caltech/JPL photochemical diffusive model for the atmosphere of Jupiter, we find that the photolysis efficiency of NH_2D is lower than that of NH_3 by as much as 30%. The D/H ratio in NH_2D/NH_3 for tracing the microphysics in the troposphere of Jupiter is also discussed.

We have explored the detectability of exovegetation on the surface of a terrestrial planet orbiting an M star. The exovegetation is responsible for producing a pigment-derived surface signature that is redshifted with respect to the Earth vegetation's red edge. The redshift was estimated using a model of leaf optical property spectra (Jacquemoud & Baret) combined with a 3 photon photosynthetic scheme calculated by Wolstencroft & Raven for a possible exovegetation growing on an M star planet. To study the detectability of this surface biosignature on an M star terrestrial planet, we have used the three-dimensional model developed by Tinetti et al. for the case of the Earth. This model can generate disk-averaged spectra and broadband integrated fluxes, which will be useful for future terrestrial planet exploration missions, such as the NASA Terrestrial Planet Finder Coronagraph. Input to this model were the atmospheric profiles and cloud distributions predicted by Joshi and coworkers for a synchronous planet orbiting an M dwarf and the distinctive surface reflectance of the exovegetation. While on Earth this pigment-derived surface feature would be almost completely masked by water absorption, even in a cloud-free atmosphere, we found that the strength of the edge feature on our simulated M star terrestrial planet can exceed that on Earth, given the right conditions. Obviously, the detectability of such biosignatures would be highly dependent on the extent of vegetation surface area, cloud cover, and viewing angle.

The close-in extrasolar giant planets (CEGPs) reside in irradiated environments much more intense than that of the giant planets in our solar system. The high UV irradiance strongly influences their photochemistry and the general current view believed that this high UV flux will greatly enhance photochemical production of hydrocarbon aerosols. In this letter, we investigate hydrocarbon aerosol formation in the atmospheres of CEGPs. We find that the abundances of hydrocarbons in the atmospheres of CEGPs are significantly less than that of Jupiter except for models in which the CH$_4$ abundance is unreasonably high (as high as CO) for the hot (effective temperatures $\gtrsim 1000$ K) atmospheres. Moreover, the hydrocarbons will be condensed out to form aerosols only when the temperature-pressure profiles of the species intersect with the saturation profiles--a case almost certainly not realized in the hot CEGPs atmospheres. Hence our models show that photochemical hydrocarbon aerosols are insignificant in the atmospheres of CEGPs. In contrast, Jupiter and Saturn have a much higher abundance of hydrocarbon aerosols in their atmospheres which are responsible for strong absorption shortward of 600 nm. Thus the insignificance of photochemical hydrocarbon aerosols in the atmospheres of CEGPs rules out one class of models with low albedos and featureless spectra shortward of 600 nm., ApJL accepted

Cross sections for photoabsorption of HCl and DCl are determined in the spectral region of 135-232 nm using radiation from a synchrotron light source. At wavelengths near the onset of absorption (λ > 200 nm), cross sections of HCl are approximately 5-10 times larger than those of DCl. These data are used to calculate rates of photodissociation of HCl and DCl in the Venusian atmosphere. For the entire wavelength region measured, the rate of photodissociation of DCl is only 16% that of HCl. The difference in rates of photodissociation contributes to the exceptionally large [D]/[H] ratio of the Venusian atmosphere.

We present 50 nights of polarimetric observations of HD 189733 in $B$ band using the POLISH2 aperture-integrated polarimeter at the Lick Observatory Shane 3-m telescope. This instrument, commissioned in 2011, is designed to search for Rayleigh scattering from short-period exoplanets due to the polarized nature of scattered light. Since these planets are spatially unresolvable from their host stars, the relative contribution of the planet-to-total system polarization is expected to vary with an amplitude of order 10 parts per million (ppm) over the course of the orbit. Non-zero and also variable at the 10 ppm level, the inherent polarization of the Lick 3-m telescope limits the accuracy of our measurements and currently inhibits conclusive detection of scattered light from this exoplanet. However, the amplitude of observed variability conservatively sets a $3 \sigma$ upper limit to the planet-induced polarization of the system of 58 ppm in $B$ band, which is consistent with a previous upper limit from the POLISH instrument at the Palomar Observatory 5-m telescope (Wiktorowicz 2009). A physically-motivated Rayleigh scattering model, which includes the depolarizing effects of multiple scattering, is used to conservatively set a $3 \sigma$ upper limit to the geometric albedo of HD 189733b of $A_g < 0.37$. This value is consistent with the value $A_g = 0.226 \pm 0.091$ derived from occultation observations with HST STIS (Evans et al. 2013), but it is inconsistent with the large $A_g = 0.61 \pm 0.12$ albedo reported by (Berdyugina et al. 2011)., Comment: 10 pages, 9 figures, submitted to ApJ

Deep extreme ultraviolet spectrograph exposures of the plasma sheet at the orbit of Europa, obtained in 2001 using the Cassini Ultraviolet Imaging Spectrograph experiment, have been analyzed to determine the state of the gas. The results are in basic agreement with earlier results, in particular with Voyager encounter measurements of electron density and temperature. Mass loading rates and lack of detectable neutrals in the plasma sheet, however, are in conflict with earlier determinations of atmospheric composition and density at Europa. A substantial fraction of the plasma species at the Europa orbit are long-lived sulfur ions originating at Io, with ~25% derived from Europa. During the outward radial diffusion process to the Europa orbit, heat deposition forces a significant rise in plasma electron temperature and latitudinal size accompanied with conversion to higher order ions, a clear indication that mass loading from Europa is very low. Analysis of far ultraviolet spectra from exposures on Europa leads to the conclusion that earlier reported atmospheric measurements have been misinterpreted. The results in the present work are also in conflict with a report that energetic neutral particles imaged by the Cassini ion and neutral camera experiment originate at the Europa orbit. An interpretation of persistent energetic proton pitch angle distributions near the Europa orbit as an effect of a significant population of neutral gas is also in conflict with the results of the present work. The general conclusion drawn here is that Europa is geophysically far less active than inferred in previous research, with mass loading of the plasma sheet ≤4.5 x 10^(25) atoms s^(-1) two orders of magnitude below earlier published calculations. Temporal variability in the region joining the Io and Europa orbits, based on the accumulated evidence, is forced by the response of the system to geophysical activity at Io. No evidence for the direct injection of H_2O into the Europa atmosphere or from Europa into the magnetosphere system, as has been observed at Enceladus in the Saturn system, is obtained in the present investigation.

Secondary eclipse spectroscopy provides invaluable insights into the temperatures and compositions of exoplanetary atmospheres. We carry out a systematic temperature and abundance retrieval analysis of nine exoplanets (HD189733b, HD209458b, HD149026b, GJ436b, WASP-12b, WASP-19b, WASP-43b, TrES-2b, and TrES-3b) observed in secondary eclipse using a combination of space- and ground-based facilities. Our goal with this analysis is to provide a consistent set of temperatures and compositions from which self-consistent models can be compared and to probe the underlying processes that shape these atmospheres. This paper is the second in a three part series of papers exploring the retrievability of temperatures and abundances from secondary eclipse spectra and the implications of these results for the chemistry of exoplanet atmospheres. In this investigation we present a catalogue of temperatures and abundances for H$_2$O, CH$_4$, CO, and CO$_2$. We find that our temperatures and abundances are generally consistent with those of previous studies, although we do not find any statistically convincing evidence for super-solar C to O ratios (e.g., solar C/O falls in the 1-sigma confidence intervals in eight of the nine planets in our sample). Furthermore, within our sample we find little evidence for thermal inversions over a wide range of effective temperatures (with the exception of HD209458b), consistent with previous investigations. The lack of evidence for inversions for most planets in our sample over such a wide range of effective temperatures provides additional support for the hypothesis that TiO is unlikely to be the absorber responsible for the formation of these inversions., Comment: Accepted to ApJ

Chemical disequilibrium has recently become a relevant topic in the study of the atmospheres of of transiting extrasolar planets, brown dwarfs, and directly imaged exoplanets. We present a new way of assessing whether or not a Jovian-like atmosphere is in chemical disequilibrium from observations of detectable or inferred gases such as H$_2$O, CH$_4$, CO, and H$_2$. Our hypothesis, based on previous kinetic modeling studies, is that cooler atmospheres will show stronger signs of disequilibrium than hotter atmospheres. We verify this with chemistry-transport models and show that planets with temperatures less than $\sim$1200 K are likely to show the strongest signs of disequilibrium due to the vertical quenching of CO, and that our new approach is able to capture this process. We also find that in certain instances a planetary composition may appear in equilibrium when it actually is not due to the degeneracy in the shape of the vertical mixing ratio profiles. We determine the state of disequilibrium in eight exoplanets using the results from secondary eclipse temperature and abundance retrievals. We find that all of the planets in our sample are consistent with thermochemical equilibrium to within 3-sigma. Future observations are needed to further constrain the abundances in order to definitively identify disequilibrium in exoplanet atmospheres., submitted to ApJ

We systematically investigated the solvable analytical benchmark cases in both one- and two-dimensional (1D and 2D) chemical-advective-diffusive systems. We use the stratosphere of Jupiter as an example but the results can be applied to other planetary atmospheres and exoplanetary atmospheres. In the 1D system, we show that CH_4 and C_2H_6 are mainly in diffusive equilibrium, and the C_2H_2 profile can be approximated by modified Bessel functions. In the 2D system in the meridional plane, analytical solutions for two typical circulation patterns are derived. Simple tracer transport modeling demonstrates that the distribution of a short-lived species (such as C_2H_2) is dominated by the local chemical sources and sinks, while that of a long-lived species (such as C_2H_6) is significantly influenced by the circulation pattern. We find that an equator-to-pole circulation could qualitatively explain the Cassini observations, but a pure diffusive transport process could not. For slowly rotating planets like the close-in extrasolar planets, the interaction between the advection by the zonal wind and chemistry might cause a phase lag between the final tracer distribution and the original source distribution. The numerical simulation results from the 2D Caltech/JPL chemistry-transport model agree well with the analytical solutions for various cases.

We introduce a new thermochemical kinetics and photochemical model. We use high-temperature bidirectional reaction rates for important H, C, O and N reactions (most importantly for CH$_4$ to CO interconversion), allowing us to attain thermochemical equilibrium, deep in an atmosphere, purely kinetically. This allows ab initio chemical modeling of an entire atmosphere, from deep-atmosphere thermochemical equilibrium to the photochemically dominated regime. We use our model to explore the atmospheric chemistry of cooler ($T_{eff} < 10^3$ K) extrasolar giant planets. In particular, we choose to model the nearby hot Neptune GJ436b, the only planet in this temperature regime for which spectroscopic measurements and estimates of chemical abundances now exist. Recent {\it Spitzer} measurements with retrieval have shown that methane is driven strongly out of equilibrium and is deeply depleted on the dayside of GJ 436b, whereas quenched carbon monoxide is abundant. This is surprising because GJ 436b is cooler than many of the heavily irradiated hot Jovians and thermally favorable for CH$_4$, and thus requires an efficient mechanism for destroying it. We include realistic estimates of ultraviolet flux from the parent dM star GJ 436, to bound the direct photolysis and photosensitized depletion of CH$_4$. While our models indicate fairly rich disequilibrium conditions are likely in cooler exoplanets over a range of planetary metallicities, we are unable to generate the conditions for substantial CH$_4$ destruction. One possibility is an anomalous source of abundant H atoms between 0.01-1 bars (which attack CH$_4$), but we cannot as yet identify an efficient means to produce these hot atoms.

Isotope effects in the non-dissociative photoionization of molecular nitrogen (N_2 + hν → N_2^+ + e^−) may play a role in determining the relative abundances of isotopic species containing nitrogen in interstellar clouds and planetary atmospheres but have not been previously measured. Measurements of the photoionization efficiency spectra of ^(14)N^2, ^(15)N^(14)N, and ^(15)N_2 from 15.5 to 18.9 eV (65.6–80.0 nm) using the Advanced Light Source at Lawrence Berkeley National Laboratory show large differences in peak energies and intensities, with the ratio of the energy-dependent photoionization cross sections, σ(^(14)N_2)/σ (^(15)N^(14)N), ranging from 0.4 to 3.5. Convolving the cross sections with the solar flux and integrating over the energies measured, the ratios of photoionization rate coefficients are J(^(15)N^(14)N)/J(^(14)N_2) = 1.00 ± 0.02 and J(^(15)N_2)/J(^(14)N_2) = 1.00 ± 0.02, suggesting that isotopic fractionation between N_2 and N_2^+ should be small under such conditions. In contrast, in a one-dimensional model of Titan’s atmosphere, isotopic self-shielding of ^(14)N_2 leads to values of J(^(15)N^(14)N)/J(^(14)N_2) as large as ~1.17, larger than under optically thin conditions but still much smaller than values as high as ~29 predicted for N_2 photodissociation. Since modeled photodissociation isotope effects overpredict the HC^(15)N/HC^(14)N ratio in Titan’s atmosphere, and since both N atoms and N_2^+ ions may ultimately lead to the formation of HCN, estimates of the potential of including N_2 photoionization to contribute to a more quantitative explanation of ^(15)N/^(14)N for HCN in Titan’s atmosphere are explored.

A study is made of the UV reflection spectrum of Jupiter as measured by the International Ultraviolet Explorer. Detailed modeling reveals the mixing ratios of C_2H_2, C_2H_6, and C_4H_2 to be (1.0 ± 0.1) x 10^(-1), (6.6 ± 5.3) x 10^(-6), and (2.9 ± 2.0) x 10^(-10), respectively, in the pressure region between ~3 and 40 mbar. Upper limits in this pressure region for the mixing ratios of C_2H_4 and NH_3 were determined to be (3.9^(+4.9)_(-3.9))x10^(-10) and (4.2^(+6.7)_(-4.2))x10^(-9), respectively. An upper limit to the optical depth of dust above the tropopause, assuming it is well mixed, is 0.2^(+0.3)_(-1.4), and an upper limit on the dayglow emission by the Lyman bands of H_2 is 1.4^(+2.4)_(-1.4) kR. Comparison with Voyager results suggests that the scale height of C_2H_2 in the region 150-10 mbar is approximately twice that of the bulk atmosphere, consistent with the IUE observation of cosine-like limb darkening in the north-south direction on Jupiter in this spectral range. These results are of use in the photochemical modeling of the upper atmosphere of Jupiter.

A photochemical theory is proposed for producing complex polymers in a methane atmosphere. It is argued that the polyacetylenes (C_(2n)H_2) are the most likely precursor molecules for the formation of the stratospheric haze layer on Titan. The production of polyacetylenes involves a strong positive feedback, leading to more production of polyactylenes. The thermosphere of Titan may undergo substantial expansion and contraction over a solar cycle, with important consequences for the chemistry of the upper atmosphere.