Modelling the VUV emission spectrum of N2: preliminary results on the effects of rotational interactions on line intensities

A theoretical model of the excited singlet ungerade electronic states of the nitrogen molecule is presented. This work is an extension of a previous study (D. Stahel, M. Leoni and K. Dressler, J. Chem. Phys. 79, 2541-2558, 1983) with the addition of rotational interactions between states of different symmetry. These rotational interactions together with the homogeneous couplings frequently lead to extreme mixing of the states. This model is being used to analyse the high resolution vacuum ultraviolet emission spectrum which is currently being recorded photoelectrically. The ultimate goal of this work is the reliable interpretation of the low resolution emission spectra observed from planetary atmospheres, notably that of Titan, and the transitions assigned as being important in the Voyager 1 spectra of Titan are discussed in detail.     

Measurements of methane absorption by the descent imager/spectral radiometer (DISR) during its descent through Titan's atmosphere

New low-temperature methane absorption coefficients pertinent to the Titan environment are presented as derived from the Huygens DISR spectral measurements combined with the in-situ measurements of the methane gas abundance profile measured by the Huygens Gas Chromatograph/Mass Spectrometer (GCMS). The visible and near-infrared spectrometers of the descent imager/spectral radiometer (DISR) instrument on the Huygens probe looked upward and downward covering wavelengths from 480 to 1620 nm at altitudes from 150 km to the surface during the descent to Titan's surface. The measurements at continuum wavelengths were used to determine the vertical distribution, single-scattering albedos, and phase functions of the aerosols. The gas chromatograph/mass spectrometer (GCMS) instrument on the probe measured the methane mixing ratio throughout the descent. The DISR measurements are the first direct measurements of the absorbing properties of methane gas made in the atmosphere of Titan at the pathlengths, pressures, and temperatures that occur there. Here we use the DISR spectral measurements to determine the relative methane absorptions at different wavelengths along the path from the probe to the sun throughout the descent. These transmissions as functions of methane path length are fit by exponential sums and used in a haze radiative transfer model to compare the results to the spectra measured by DISR. We also compare the recent laboratory measurements of methane absorption at low temperatures [Irwin et al., 2006. Improved near-infrared methane band models and k-distribution parameters from 2000 to 9500 cm⁻¹ and implications for interpretation of outer planet spectra. Icarus 181, 309-319] with the DISR measurements. We find that the strong bands formed at low pressures on Titan act as if they have roughly half the absorption predicted by the laboratory measurements, while the weak absorption regions absorb considerably more than suggested by some extrapolations of warm measurements to the cold Titan temperatures. We give factors as a function of wavelength that can be used with the published methane coefficients between 830 and 1620 nm to give agreement with the DISR measurements. We also give exponential sum coefficients for methane absorptions that fit the DISR observations. We find the DISR observations of the weaker methane bands shortward of 830 nm agree with the methane coefficients given by Karkoschka [1994. Spectrophotometry of the jovian planets and Titan at 300- to 1000-nm wavelength: the methane spectrum. Icarus 111, 174-192]. Finally, we discuss the implications of our results for computations of methane absorption in the atmospheres of the outer planets.     

The binary collision-induced second overtone band of gaseous hydrogen: modelling and laboratory measurements

Collision-induced absorption (CIA) is the major source of the infrared opacity of dense planetary atmospheres which are composed of nonpolar molecules. Knowledge of CIA absorption spectra of H₂–H₂ pairs is important for modelling the atmospheres of planets and cold stars that are mainly composed of hydrogen. The spectra of hydrogen in the region of the second overtone at 0.8 μm have been recorded at temperatures of 298 and 77.5 K for gas densities ranging from 100 to 800 amagats. By extrapolation to zero density of the absorption coefficient measured every 10 cm⁻¹ in the spectral range from 11,100 to 13,800 cm⁻¹, we have determined the binary absorption coefficient. These extrapolated measurements are compared with calculations based on a model that was obtained by using simple computer codes and lineshape profiles. In view of the very weak absorption of the second overtone band, we find the agreement between results of the model and experiment to be reasonable.     

Clues on the importance of comets in the origin and evolution of the atmospheres of Titan and Earth

Earth and Titan are two planetary bodies formed far from each other. Nevertheless the chemical composition of their atmospheres exhibits common indications of being produced by the accretion, plus ulterior in-situ processing of cometary materials. This is remarkable because while the Earth formed in the inner part of the disk, presumably from the accretion of rocky planetesimals depleted in oxygen and exhibiting a chemical similitude with enstatite chondrites, Titan formed within Saturn's sub-nebula from oxygen- and volatile-rich bodies, called cometesimals. From a cosmochemical and astrobiological perspective, the study of the H, C, N, and O isotopes on Earth and Titan could be the key to decipher the processes occurred in the early stages of formation of both planetary bodies. The main goal of this paper is to quantify the presumable ways of chemical evolution of both planetary bodies, in particular the abundance of CO and N₂ in their early atmospheres. In order to do that the primeval atmospheres and evolution of Titan and Earth have been analyzed from a thermodynamic point of view. The most relevant chemical reactions involving these species and presumably important at their early stages are discussed. Then, we have interpreted the results of this study in light of the results obtained by the Cassini–Huygens mission on these species and their isotopes. Given that H, C, N, and O were preferentially depleted from inner disk materials that formed our planet, the observed similitude of their isotopic fractionation, and subsequent close evolution of Earth's and Titan's atmospheres points towards a cometary origin of Earth atmosphere. Consequently, our scenario also supports the key role of late veneers (comets and water-rich carbonaceous asteroids) enriching the volatile content of the Earth at the time of the late heavy bombardment of terrestrial planets.     

Refractive index measurements of ammonia and hydrocarbon ices at 632.8 nm

Optical constants in a broad temperature and wavelength range are important input parameters in radiative transfer models used in studies of planetary atmospheres. In the laboratory, the refractive index values of ices at the HeNe laser wavelength (632.8 nm) are often used to monitor the growth rate and thickness of ice films. In this report we present laboratory measurements determining the refractive index at 632.8 nm of ammonia and hydrocarbon ices in the temperature range 80-100 K. Thin ice films are vapor-deposited on a cryogenically cooled mirror located inside a high-vacuum apparatus. The real component of the refractive index of these ice films is determined by a two-angle interferometric technique. Optical modeling calculations of the transmittance and reflectance through the thin ice films assist in the interpretation of the experimental results. We discuss our results and compare them with other measurements available in the literature. The results reported here are relevant to the spectroscopy of icy objects in the solar system; they are needed to perform laboratory characterization of ices, derive optical constants, and model spectra.     

Near-IR methane absorption in outer planet atmospheres: Improved models of temperature dependence and implications for Uranus cloud structure

Near-IR absorption of methane in the 2000-9500 cm⁻¹ spectral region plays a major role in outer planet atmospheres. However, the theoretical basis for modeling the observations of reflectivity and emission in these regions has had serious uncertainties at temperatures needed for interpreting observations of the colder outer planets. A lack of line parameter information, including ground-state energies and the absence of weak lines, limit the applicability of line-by-line calculations at low temperatures and for long path lengths, requiring the use of band models. However, prior band models have parameterized the temperature dependence in a way that cannot be accurately extrapolated to low temperatures. Here we use simulations to show how a new parameterization of temperature dependence can greatly improve band model accuracy and allow extension of band models to the much lower temperatures that are needed to interpret observations of Uranus, Neptune, Titan, and Saturn. Use of this new parameterization by Irwin et al. [Irwin, P.G.J., Sromovsky, L.A., Strong, E.K., Sihra, K., Bowles, N., Calcutt, S.B., 2005b. Icarus. In press] has verified improved fits to laboratory observations of Strong et al. [Strong, K., Taylor, F.W., Calcutt, S.B., Remedios, J.J., Ballard, J., 1993. J. Quant. Spectrosc. Radiat. Trans. 50, 363-429] and Sihra [1998. Ph.D. Thesis, Univ. of Oxford], which cover the temperature range from 100 to 340 K. Here we compare model predictions to 77 K laboratory observations and to Uranus spectra, which show much improved agreement between observed and modeled spectral features, allowing tighter constraints on pressure levels of Uranus cloud particles, implying that most scattering contributions arise from pressures near 2 bars and 6 bars rather than expected pressures near 1.25 and 3.1 bars. Between visible and near-IR wavelengths, both cloud layers exhibit strong decreases in reflectivity that are indicative of low opacity and submicron particle sizes.     

Crossed molecular beam study of gas phase reactions relevant to the chemistry of planetary atmospheres: The case of C2+C2H2

The reaction between dicarbon (C₂) and acetylene was recently suggested as a possible competitive reaction in the atmospheres of Titan, Saturn and Uranus by rate constant measurements at very low temperatures [see Canosa, A., Páramo, A., Le Picard, S.D., Sims, I.R., 2007. An experimental study of the reaction kinetics of C₂(X¹Σ_g⁺) with hydrocarbons (CH₄, C₂H₂, C₂H₄, C₂H₆ and C₃H₈) over the temperature range 24-300 K: implications for the atmospheres of Titan and the Giant Planets. Icarus 187, 558-568]. We have investigated the reaction of the two low lying electron states of C₂ and acetylene by the crossed molecular beam (CMB) technique with mass spectrometric detection. C₄H, already identified as a primary product in previous CMB experiments, is confirmed as such, even though the mechanism of formation is inferred to be partly different with respect to the previous study. An experimental setup has been devised to characterize the internal population of C₂ and refine the interpretation of the scattering results. The implications for the modelling of the atmospheres of Giant Planets and Titan, as well as cometary comae and the interstellar medium, are discussed.     

Spectra of simulated lightning on Venus,Jupiter, and Titan

Laser-induced plasmas in various gas mixtures were used to simulate lightning in other planetary atmospheres. This method of simulation has the advantage of producing short-duration, high-temperature plasmas free from electrode contamination. The laser-induced plasma discharges in air are shown to accurately simulate terrestrial lightning and can be expected to simulate lightning spectra in other planetary atmospheres. Spectra from 240 to 880 nm are presented for simulated lightning in the atmospheres of Venus, Earth, Jupiter, and Titan. The spectra of lightning on the other giant planets are expected to be similar to that of Jupiter because the atmospheres of these planets are composed mainly of hydrogen and helium. The spectra of Venus and Titan show substantial amounts of radiation due to the presence of carbon atoms and ions and show CN Violet radiation. Although small amounts of CH₄ and NH₃ are present in the Jovian atmosphere, only emission from hydrogen and helium is observed. Most differences in the spectra can be understood in terms of the elemental ratios of the gas mixtures. Consequently, observations of the spectra of lightning on other planets should provide in situ estimates of the atmospheric and aerosol composition in the cloud layers in which lightning is occuring. In particular, the detection of inert gases such as helium should be possible and the relative abundance of these gases compared to major constituents might be determined.     

Reflectance spectra of hydrated Titan tholins at cryogenic temperatures and implications for compositional interpretation of red objects in the outer Solar System

We report the visible and near-infrared (0.4-2.5 μm) laboratory bidirectional reflectance of hydrated Titan tholin at cryogenic temperatures (∼100-300 K). When compared with room temperature measurements, the visible and near-infrared color of hydrated Titan tholin becomes bluer by ∼14% at low temperatures in the 0.7-1.0 μm region. Assuming the observed color changes are representative of tholin-like materials we estimate the influence of such color changes on the interpretation of the Centaur Pholus and find that the modest color changes will not significantly alter existing interpretations.     

FT-IR measurements of cold C3H8 cross sections at 7–15 μm for Titan atmosphere

We present absorption cross sections of propane (C₃H₈) at temperatures from 145 K to 297 K in the 690–1550 cm⁻¹ region. Pure and N₂-broadened spectra were measured at pressures from 3 Torr to 742 Torr using a Bruker IFS125 FT-IR spectrometer at JPL. The gas absorption cell, developed at Connecticut College, was cooled by a closed-cycle helium refrigerator. The cross sections were measured and compiled for individual spectra recorded at various experimental conditions covering the planetary atmosphere and Titan. In addition to the cross sections, a propane pseudoline list with a frequency grid of 0.005 cm⁻¹, was fitted to the 34 laboratory spectra. Line intensities and lower state energies were retrieved for each line, assuming a constant width. Validation tests showed that the pseudoline list reproduces discrete absorption features and continuum, the latter contributed by numerous weak and hot band features, in most of the observed spectra within 3%. Based on the pseudoline list, the total intensity in the 690–1550 cm⁻¹ region was determined to be 52.93 (±3%) × 10⁻¹⁹ cm⁻¹/(molecule cm⁻²) at 296 K; this value is within 3% of the average from four earlier studies. Finally, the merit of the pseudoline approach is addressed for heavy polyatomic molecules in support of spectroscopic observation of atmospheres of Titan and other planets. The cold cross sections will be submitted to the HITRAN database (hitran.harvard.edu), and the list of C₃H₈ pseudolines will be available from a MK-IV website of JPL (http://mark4sun.jpl.nasa.gov/data/spec/Pseudo).     

Absorption coefficients for the 727 nm band of methane at 77 K determined by intracavity laser spectroscopy

Methane spectral features in the visible to near-IR region are prominent in the spectra of the outer planets but laboratory data for the appropriate methane conditions are required to interpret the observational data. By use of the intracavity laser spectroscopy technique, a moderately high resolution (500,000) absorption spectrum of the 727 nm band of methane at 77 K is obtained. The methane absorption bands in the visible to near-IR region are very weak, but intracavity laser spectroscopy provides sufficient sensitivity to perform the measurements and to extract quantitative data for methane at low temperatures. Absorption coefficients are determined and are reported as averages at one Å intervals throughout the region 7127–7420 Å. By integrating over the band, an intensity of 753 cm^–1 km^–1 am^–1 is obtained. The results compare well with previous low resolution measurements on methane at room temperature, with gas phase results calculated using the absorption spectrum of liquid methane, and with absorption coefficients derived from methane features observed in the spectra of the outer planets and Titan.     

Infrared spectroscopy of crystalline and amorphous diacetylene (C4H2) and implications for Titan's atmospheric composition

New laboratory spectra of crystalline and amorphous diacetylene ice have been recorded in the range of 7000-500 cm⁻¹ (1.4-20 μm) to aid in the identification of solid diacetylene on Saturn's moon Titan. We have established that amorphous diacetylene ice is stable only at temperatures less than 70±1 K. With respect to observations on Titan, the best approach would be to utilize future space-based telescopes to search for the ν₄ (3277/3271 cm⁻¹) in absorption against the reflected light from the sun and the slightly weaker ν₈ absorption bands (676/661 cm⁻¹) in absorption against the continuum emission.     

Atmospheric acoustics of Titan, Mars, Venus, and Earth

Planetary atmospheres are complex dynamical systems whose structure, composition, and dynamics intimately affect the propagation of sound. Thus, acoustic waves, being coupled directly to the medium, can effectively probe planetary environments. Here we show how the acoustic absorption and speed of sound in the atmospheres of Venus, Mars, Titan, and Earth (as predicted by a recent molecular acoustics model) mirror the different environments. Starting at the surface, where the sound speed ranges from ∼200 m/s for Titan to ∼410 m/s for Venus, the vertical sound speed profiles reveal differences in the atmospheres' thermal layering and composition. The absorption profiles are relatively smooth for Mars, Titan, and Earth while Venus stands out with a noticeable attenuation dip occurring between 40 and 100 km. We also simulate a descent module sampling the sound field produced by a low-frequency “event” near the surface noting the occurrence of acoustic quiet zones.     

Near-infrared spectroscopic search for the close orbiting planet HD 75289b

We present a search for the near-infrared spectroscopic signature of the close orbiting extrasolar giant planet HD 75289b. We obtained ∼230 spectra in the wavelength range 2.18–2.19 μm using the Phoenix spectrograph at Gemini South. By considering the direct spectrum, derived from irradiated model atmospheres, we search for the absorption profile signature present in the combined star and planet light. Since the planetary spectrum is separated from the stellar spectrum at most phases, we apply a phase-dependent orbital model and tomographic techniques to search for absorption signatures.
Because the absorption signature lies buried in the noise of a single exposure we apply a multiline deconvolution to the spectral lines available in order to boost the effective signal-to-noise ratio (S/N) of the data. The wavelength coverage of 80 Å is expected to contain ∼100 planetary lines, enabling a mean line with S/N of 800 to be achieved after deconvolution. We are nevertheless unable to detect the presence of the planet in the data and carry out further simulations to show that broader wavelength coverage should enable a planet like HD 75289b to be detected with 99.9 per cent confidence. We investigate the sensitivity of our method and estimate detection tolerances for mismatches between observed and model planetary atmospheres.     

The vibrational overtone spectrum of liquid methane in the visible and near infrared: Applications to planetary studies

The strengths of 10 bands in the absorption spectrum of liquid methane betwen 19 400 and 6190 Å have been measured. After a small correction for the polarizability of the liquid is applied, for the purpose of comparison with similar gas phase measurements, it is found that there is no temperature dependence of the band strengths between 95 and 295°K. Changes of band shape with temperature cause the 95°K laboratory spectra to resemble Saturn more than room temperature observations do. Gas phase absorption clearly dominates the liquid in planetary spectra, so liquid methane cannot be detected in the outer Solar System by Earth-based observations.     

Continuum beyond the Lyman limit and effective temperatures of the nuclei of planetary nebulae

Using published data on Hß-,λ4471 Hel- and λ4686 Hell-line fluxes for planetary nebulae the energy distribution in their nuclei is calculated in the wavelength range 100–912 Å by supposing that 1) the spectrum inclination is the same in the regions of continuous absorption of Hl, Hel, and Hell atoms; and 2) discontinuities at 504 Å and 228 Å are present in the nuclei spectra. From 40 investigated nebulae, only for two nuclei the distribution in all three intervals 504–912 Å, 228–504 Å and λ ≦ 228 Å corresponds to one and the same temperature of black-body emission. In 24 cases the emission temperature is the same for the first and the second interval. The energy distribution in the wavelength range shorter than 228 Å corresponds systematically to very high temperatures T_* > 100,000 K. It is concluded that the emission temperature over the surface of nuclei is markedly inhomogeneous and/or the nuclei of planetary nebulae possess a hot corona.     

Polycyclic aromatic hydrocarbons in the atmospheres of Titan and Jupiter

Polycyclic aromatic hydrocarbons (PAHs) are important components of the interstellar medium and carbonaceous chondrites, but have never been identified in the reducing atmospheres of the outer solar system. Incompletely characterized complex organic solids (tholins) produced by irradiating simulated Titan atmospheres reproduce well the observed UV/visible/IR optical constants of the Titan stratospheric haze. Titan tholin and a tholin generated in a crude simulation of the atmosphere of Jupiter are examined by two-step laser desorption/multiphoton ionization mass spectrometry. A range of two- to four-ring PAHs, some with one to four alkylation sites are identified, with net abundance approximately 10(-4) g g-1 (grams per gram) of tholins produced. Synchronous fluorescence techniques confirm this detection. Titan tholins have proportionately more one- and two-ring PAHs than do Jupiter tholins, which in turn have more four-ring and larger PAHs. The four-ringed PAH chrysene, prominent in some discussions of interstellar grains, is found in Jupiter tholins. Solid state 13C NMR spectroscopy suggests approximately equal to 25% of the total C in both tholins is tied up in aromatic and/or aliphatic alkenes. IR spectra indicate an upper limit in both tholins of approximately equal to 6% by mass in benzenes, heterocyclics, and PAHs with more than four rings. Condensed PAHs may contribute at most approximately 10% to the observed detached limb haze layers on Titan. As with interstellar PAHs, the synthesis route of planetary PAHs is likely to be via acetylene addition reactions.     

Temperature dependence of HC3N,C6H2, and C4N2 mid-UV absorption coefficients. Application to the interpretation of Titan's atmospheric spectra

Three organic compounds (HC₃N, C₆H₂, and C₄N₂) relevant of Titan's atmosphere have been studied within the framework of the SIPAT (Spectroscopie UV d'Intérêt Prébiologique dans l'Atmosphère de Titan) program. Since this facility is still unable to reach the very low temperatures (170 K) of Titan's high atmosphere, spectra have to be obtained at several absorption-cell temperatures, and the data extrapolated towards lower temperatures. Previously published HC₃N and C₆H₂ absorption coefficient data are reviewed, while new spectroscopic data are presented on C₄N₂. Integrated intensity calculations over the vibrational bands are performed apart from the background continuum. Thus, only the band contrast is considered here. While, the temperature dependence of the hot-band integrated intensity follows a Boltzmann distribution, we have enhanced the fit through an empirical parametrisation to account for the observed temperature dependence of the C₄N₂ and HC₃N absorption coefficients, and to extrapolate those data to the low temperature conditions of Titan's high atmosphere. Finally, we discuss the implications of the results to possible detection by remote sensing observations of these minor compounds in Titan's atmosphere.     

A random graphs model for the study of chemical complexity in planetary atmospheres

We suggest that the study of the general behavior of a chemical system in planetary atmospheres might be equivalent to the study of the evolution of connected components in a random graphs model. The main result of our model is that interacting elements in a system self-organize in such a way that the distribution in size of the created compounds follows a power-law relation. We show that hydrocarbons in giant planets and Titan atmospheres might follow the same type of distribution, suggesting that atmospheric photochemical systems might self-organized as random graphs do. This property could give a new and predictive method for investigations of chemical complexity in planetary atmospheres.