Search

Rovibronic energy levels are determined for four low-lying electronic states (\X, \A, \Sa, and \Sc) of the imidogen free radical ($^{14}$NH) using the \Marvel\ (Measured Active Rotational-Vibrational Energy Levels) technique. Compilation of transitions from both laboratory measurements and solar spectra, found in 18 publications, yields a dataset of 3002 rovibronic transitions forming elements of a measured spectroscopic network (SN). At the end of the MARVEL procedure, the majority of the transitions form a single, self-consistent SN component of 2954 rovibronic transitions and 1058 energy levels, \NoX, \NoA, and \Noc\ for the \X, \A, and \Sc\ electronic states, respectively. The \Sa\ electronic state is characterized by \Noa\ $\Lambda$-doublet levels, counting each level only once. Electronic structure computations show that unusually the CCSD(T) method does not accurately predict the \Sa\ excitation energy even at the complete basis set limit.

The carbon dimer, the $^{12}$C$_2$ molecule, is ubiquitous in astronomical environments. Experimental-quality rovibronic energy levels are reported for $^{12}$C$_2$, based on rovibronic transitions measured for and among its singlet, triplet, and quintet electronic states, reported in 42 publications. The determination utilizes the Measured Active Rotational-Vibrational Energy Levels (MARVEL) technique. The 23,343 transitions measured experimentally and validated within this study determine 5,699 rovibronic energy levels, 1,325, 4,309, and 65 levels for the singlet, triplet, and quintet states investigated, respectively. The MARVEL analysis provides rovibronic energies for six singlet, six triplet, and two quintet electronic states. For example, the lowest measurable energy level of the \astate\ state, corresponding to the $J=2$ total angular momentum quantum number and the $F_1$ spin-multiplet component, is 603.817(5) \cm. This well-determined energy difference should facilitate observations of singlet--triplet intercombination lines which are thought to occur in the interstellar medium and comets. The large number of highly accurate and clearly labeled transitions that can be derived by combining MARVEL energy levels with computed temperature-dependent intensities should help a number of astrophysical observations as well as corresponding laboratory measurements. The experimental rovibronic energy levels, augmented, where needed, with {\it ab initio} variational ones based on empirically adjusted and spin-orbit coupled potential energy curves obtained using the \Duo\ code, are used to obtain a highly accurate partition function, and related thermodynamic data, for $^{12}$C$_2$ up to 4,000 K., Comment: ApJ Supplements (in press), 48 pages

The current report covers the period from the second half of 2011 to late 2014. It is divided into three areas covering rotational, vibrational, and electronic spectroscopy. A signifcant amount of experimental and theoretical work has been accomplished over the past three years, leading to the development and expansion of a number of databases whose links are provided below. Two notable publications have appeared recently: An issue of The Journal of Physical Chemistry A in 2013 honoring the many contributions of Takeshi Oka (J. Phys. Chem. A, 117, pp. 9305-10143); and IAU Symposium 297 on Diffuse Interstellar Bands. A number of the relevant papers from these volumes are cited. Related research on collisions, reactions on grain surfaces, and astrochemistry are not included here., Comment: TRIENNIAL REPORT 2012-2015, 16 pages, to be published in Transactions IAU, Volume 29A, Reports on Astronomy 2012-2015, Thierry Montmerle, ed

Hot methane is found in many "cool" sub-stellar astronomical sources including brown dwarfs and exoplanets, as well as in combustion environments on Earth. We report on the first high-resolution laboratory absorption spectra of hot methane at temperatures up to 1200 K. Our observations are compared to the latest theoretical spectral predictions and recent brown dwarf spectra. The expectation that millions of weak absorption lines combine to form a continuum, not seen at room temperature, is confirmed. Our high-resolution transmittance spectra account for both the emission and absorption of methane at elevated temperatures. From these spectra, we obtain an empirical line list and continuum that is able to account for the absorption of methane in high temperature environments at both high and low resolution. Great advances have recently been made in the theoretical prediction of hot methane, and our experimental measurements highlight the progress made and the problems that still remain., Comment: 9 pages, 5 figures and 3 tables. For associated online data see http://dx.doi.org/10.1088/0004-637X/813/1/12

Infrared absorption cross sections near 3.3 $\mu$m have been obtained for ethane, C$_{2}$H$_{6}$. These were acquired at elevated temperatures (up to 773 K) using a Fourier transform infrared spectrometer and tube furnace with a resolution of 0.005 cm$^{-1}$. The integrated absorption was calibrated using composite infrared spectra taken from the Pacific Northwest National Laboratory (PNNL). These new measurements are the first high-resolution infrared C$_{2}$H$_{6}$ cross sections at elevated temperatures., Comment: 9 pages, 3 figures, 3 tables. Accepted for publication in Molecular Astrophysics

A new line list including positions and absolute intensities (in the form of Einstein $A$ values and oscillator strengths) has been produced for the OH ground X\DP\ state rovibrational (Meinel system) and pure rotational transitions. All possible transitions are included with v$\primed$ and v$\Dprimed$ up to 13, and $J$ up to between 9.5 and 59.5, depending on the band. An updated fit to determine molecular constants has been performed, which includes some new rotational data and a simultaneous fitting of all molecular constants. The absolute line intensities are based on a new dipole moment function, which is a combination of two high level ab initio calculations. The calculations show good agreement with an experimental v=1 lifetime, experimental $\mu_\mathrm{v}$ values, and $\Delta$v=2 line intensity ratios from an observed spectrum. To achieve this good agreement, an alteration in the method of converting matrix elements from Hund's case (b) to (a) was made. Partitions sums have been calculated using the new energy levels, for the temperature range 5-6000 K, which extends the previously available (in HITRAN) 70-3000 K range. The resulting absolute intensities have been used to calculate O abundances in the Sun, Arcturus, and two red giants in the Galactic open and globular clusters M67 and M71. Literature data based mainly on [O I] lines are available for the Sun and Arcturus, and excellent agreement is found., Comment: 17 pages, 8 figues. 7 supplementary files: dipole moment functions (OH-X-DMFs.txt), equilibrium constants (OH-X-Equilibrium_Constants.txt), partition function (OH-X-Q_5-6000K.dat), PGOPHER file with molecular constants and transition matric elements (OH-XX.pgo), vibrational Einstein A and f values (OH-XX-Avv_fvv.txt), line list (OH-XX-Line_list.txt), and OH-Transformation_Equation_Extra.docx

Galactic open and globular clusters (OCs, GCs) appear to inhabit separate regions of the age-mass plane. However, the transition between them is not easily defined because there is some overlap between high-mass, old OCs and low-mass, young GCs. We are exploring the possibility of a clear-cut separation between OCs and GCs using an abundance feature that has been found so far only in GCs: (anti)correlations between light elements. Among the coupled abundance trends, the Na-O anticorrelation is the most widely studied. These anticorrelations are the signature of self-enrichment, i.e., of a formation mechanism that implies multiple generations of stars. Here we concentrate on the old, massive, metal-rich OC NGC 6791. We analyzed archival Keck/HIRES spectra of 15 NGC 6791 main sequence turn-off and evolved stars, concentrating on the derivation of C, N, O, and Na abundances. We also used WIYN/Hydra spectra of 21 evolved stars (one is in common). Given the spectral complexity of the very metal-rich NGC 6791 stars, we employed spectrum synthesis to measure most of the abundances. We confirmed the cluster super-solar metallicity and abundances of Ca and Ni that have been derived in past studies. More importantly, we did not detect any significant star-to-star abundance dispersion in C, N, O and Na. Based on the absence of a clear Na-O anticorrelation, NGC 6791 can still be considered a true OC, hosting a single generation of stars, and not a low-mass GC., Comment: In press on ApJ; 3 tables, 11 figures

The report of an IUPAC Task Group, formed in 2011 on "Intensities and line shapes in high-resolution spectra of water isotopologues from experiment and theory" (Project No. 2011-022-2-100), on line profiles of isolated high-resolution rotational-vibrational transitions perturbed by neutral gas-phase molecules is presented. The well-documented inadequacies of the Voigt profile (VP), used almost universally by databases and radiative-transfer codes, to represent pressure effects and Doppler broadening in isolated vibrational-rotational and pure rotational transitions of the water molecule have resulted in the development of a variety of alternative line-profile models. These models capture more of the physics of the influence of pressure on line shapes but, in general, at the price of greater complexity. The Task Group recommends that the partially Correlated quadratic-Speed-Dependent Hard-Collision profile should be adopted as the appropriate model for high-resolution spectroscopy. For simplicity this should be called the Hartmann--Tran profile (HTP). The HTP is sophisticated enough to capture the various collisional contributions to the isolated line shape, can be computed in a straightforward and rapid manner, and reduces to simpler profiles, including the Voigt profile, under certain simplifying assumptions., Comment: Accepted for publication in Pure and Applied Chemistry

Observations were made for a number of carbon-rich circumstellar envelopes using the Phoenix spectrograph on the Gemini South telescope to determine the abundance of small carbon chain molecules. Vibration-rotation lines of the $\nu_{3}$ antisymmetric stretch of C$_{3}$ near 2040 cm$^{-1}$ (4.902 $\mu$m) have been used to determine the column density for four carbon-rich circumstellar envelopes: CRL 865, CRL 1922, CRL 2023 and IRC +10216. We additionally calculate the column density of C$_{5}$ for IRC +10216, and provide an upper limit for 5 more objects. An upper limit estimate for the C$_{7}$ column density is also provided for IRC+10216. A comparison of these column densities suggest a revision to current circumstellar chemical models may be needed.

Accurate rotation-vibration line lists for two molecules, NaCl and KCl, in their ground electronic states are presented. These line lists are suitable for temperatures relevant to exoplanetary atmospheres and cool stars (up to 3000 K). Isotopologues $^{23}$Na$^{35}$Cl, $^{23}$Na$^{37}$Cl, $^{39}$K$^{35}$Cl, $^{39}$K$^{37}$Cl, $^{41}$K$^{35}$Cl and $^{41}$K$^{37}$Cl are considered. Laboratory data was used to refine ab initio potential energy curves in order to compute accurate ro-vibrational energy levels. Einstein A coefficients are generated using newly determined ab initio dipole moment curves calculated using the CCSD(T) method. New Dunham Y$_{ij}$ constants for KCl are generated by a reanalysis of a published Fourier transform infrared emission spectra. Partition functions plus full line lists of ro-vibration transitions are made available in an electronic form as supplementary data to this article and at www.exomol.com., Comment: submitted to MNRAS

We present comprehensive experimental line lists of methane (CH4) at high temperatures obtained by recording Fourier transform infrared emission spectra. Calibrated line lists are presented for the temperatures 300 - 1400 degC at twelve 100 degC intervals spanning the 960 - 5000 cm-1 (2.0 - 10.4 microns) region of the infrared. This range encompasses the dyad, pentad and octad regions, i.e., all fundamental vibrational modes along with a number of combination, overtone and hot bands. Using our CH4 spectra, we have estimated empirical lower state energies (Elow in cm-1) and our values have been incorporated into the line lists along with line positions (cm-1) and calibrated line intensities (S' in cm molecule-1). We expect our hot CH4 line lists to find direct application in the modeling of planetary atmospheres and brown dwarfs., Comment: Supplementary material is provided via the Astrophysical Journal reference

New rotational line strengths for the C2 Swan system have been calculated for vibrational bands with v'=0-10 and v"=0-9, and J values up to J=34-96, based on previous observations in 30 vibrational bands. Line positions from several sources were combined with the results from recent deperturbation studies of the v'=4 and v'=6 states, and a weighted global least squares fit was performed. We report the updated molecular constants. The line strengths are based on a recent ab initio calculation of the transition dipole moment function. A line list has been made available, including observed and calculated line positions, Einstein A coefficients and oscillator strengths (f-values). The line list will be useful for astronomers and combustion scientists who utilize C2 Swan spectra. Einstein A coefficients and f-values were also calculated for the vibrational bands of the Swan system., Comment: 23 pages, 5 figures, submitted to JQSRT, new C2 Swan line list available at http://bernath.uwaterloo.ca/download/AutoIndex.php?dir=/C2/ (C2SwanLineList2012.txt); Changes for version 2 - typo in equations 4 and 5, line list updated due to typo in code causing f-values in line list to be calculated incorrectly (all other values in list, and all values in tables are correct)

The current report covers the period from the second half of 2003 to the first half of 2011, bringing the Working Group's efforts up to date, and is divided into three main sections covering rotational, vibrational, and electronic spectroscopy. Rather than being exhaustive, space limitations only allow us to highlight a representative sample of work on molecular spectra. Related research on collisions, reactions on grain surfaces, and astrochemistry appear in the report by another Working Group. These also recount recent conferences and workshops on molecular astrophysics., Comment: Triennial Report 2009-2012, published in Transactions IAU, Volume 7, Issue T28A, p. 355-370

We present line lists for ammonia (NH$_{3}$) at high temperatures obtained by recording Fourier transform infrared emission spectra. Calibrated line lists are presented for twelve temperatures (300 -- 1300$^{\circ}$C in 100$^{\circ}$C intervals and 1370$^{\circ}$C) and each line list covers the 740 -- 2100 cm$^{-1}$ range, which includes the majority of the $\nu_{2}$ umbrella bending mode region (11 $\mu$m) and the $\nu_{4}$ asymmetric bending mode region (6.2 $\mu$m). We also demonstrate the useful technique of obtaining empirical lower state energies from a set of spectra recorded at different sample temperatures. Using our NH$_{3}$ spectra, we have estimated lower state energies ($E_{Low}$ in cm$^{-1}$) and our values have been incorporated into the line lists along with calibrated wavenumbers ($\tilde{\nu}$ in cm$^{-1}$) and calibrated line intensities ($S'$ in cm/molecule) for each line. We expect our hot NH$_{3}$ line lists to find direct application in the modelling of planetary atmospheres and brown dwarfs.

Molecular FeH provides a large number of sharp and isolated absorption lines that can be used to measure radial velocity, rotation, or magnetic field strength with high accuracy. Our aim is to provide an FeH atlas for M-type stars in the spectral region from 986 nm to 1077 nm (Wing-Ford band). To identify these lines in CRIRES spectra of the magnetically inactive, slowly rotating, M5.5 dwarf GJ1002, we calculated model spectra for the selected spectral region with theoretical FeH line data. In general this line list agrees with the observed data, but several individual lines differ significantly in position or in line strength. After identification of as many as possible FeH lines, we correct the line data for position and line strength to provide an accurate atlas of FeH absorption lines for use in high precision spectroscopy of low mass stars. For all lines, we use a Voigt function to obtain their positions and equivalent widths. Identification with theoretical lines is done by hand. For confirmation of the identified lines, we use statistical methods, cross- correlation techniques, and line intensities. Eventually, we were able to identify FeH lines from the (0, 0), (1, 0), (1, 1), (2, 1), (2, 2), (3, 2), and (4, 3) vibrational bands in the observed spectra and correct the positions of the lines if necessary. The deviations between theoretical and observed positions follow a normal distribution approximately around zero. In order to empirically correct the line strength, we determined Teff, instrumental broadening (rotational broadening) and a van der Waals enhancement factor for FeH lines in GJ1002. We also give scaling factors for the Einstein A values to correct the line strengths. With the identified lines, we derived rotational temperatures from line intensities for GJ1002. ... ., Comment: 14 pages, 16 figures, accepted for publication in A&A

The optical and infrared spectra of a wide variety of `cool' astronomical objects including the Sun, sunspots, K-, M- and S-type stars, carbon stars, brown dwarfs and extrasolar planets are reviewed. The review provides the necessary astronomical background for chemical physicists to understand and appreciate the unique molecular environments found in astronomy. The calculation of molecular opacities needed to simulate the observed spectral energy distributions is discussed.

Using previous measurements and quantum chemical calculations to derive the molecular properties of the TiH molecule, we obtain new values for its ro-vibrational constants, thermochemical data, spectral line lists, line strengths, and absorption opacities. Furthermore, we calculate the abundance of TiH in M and L dwarf atmospheres and conclude that it is much higher than previously thought. We find that the TiH/TiO ratio increases strongly with decreasing metallicity, and at high temperatures can exceed unity. We suggest that, particularly for subdwarf L and M dwarfs, spectral features of TiH near $\sim$0.52 \mic, 0.94 \mic, and in the $H$ band may be more easily measureable than heretofore thought. The recent possible identification in the L subdwarf 2MASS J0532 of the 0.94 \mic feature of TiH is in keeping with this expectation. We speculate that looking for TiH in other dwarfs and subdwarfs will shed light on the distinctive titanium chemistry of the atmospheres of substellar-mass objects and the dimmest stars., Comment: 37 pages, including 4 figures and 13 tables, accepted to the Astrophysical Journal

The recent 23-30 January and 7-11 March 2012 solar proton event (SPE) periods were substantial and caused significant impacts on the middle atmosphere. These were the two largest SPE periods of solar cycle 24 so far. The highly energetic solar protons produced considerable ionization of the neutral atmosphere as well as HOx (H, OH, HO2) and NOx (N, NO, NO2). We compute a NOx production of 1.9 and 2.1 Gigamoles due to these SPE periods in January and March 2012, respectively, which places these SPE periods among the 12 largest in the past 50 years. Aura Microwave Limb Sounder (MLS) observations of the peroxy radical, HO2, show significant enhancements of 0.9 ppbv in the northern polar mesosphere as a result of these SPE periods. Both MLS measurements and Goddard Space Flight Center (GSFC) two-dimensional (2D) model predictions indicated middle mesospheric ozone decreases of 20 percent for several days in the northern polar region with maximum depletions 60 percent as a result of the HOx produced in both the January and March 2012 SPE periods. The SCISAT-1 Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE) and the Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instruments measured NO and NO2 (NOx), which indicated enhancements of over 20 ppbv in most of the northern polar mesosphere for several days as a result of these SPE periods. The GSFC 2D model was used to predict the medium-term (months) influence and found that the polar Southern Hemisphere middle atmosphere ozone was most affected by these solar events due to the increased downward motion in the fall and early winter. The downward transport moved the SPE-produced NOy to lower altitudes and led to predicted modest destruction of ozone (5-9 percent) in the upper stratosphere days to weeks after the March 2012 event. Total ozone reductions were predicted to be a maximum of 1 percent in 2012 due to these SPEs.

We analyze the relation between atmospheric temperature and water vapor-a fundamental component of the global climate system-for stratospheric water vapor (SWV). We compare measurements of SWV (and methane where available) over the period 1980-2011 from NOAA balloon-borne frostpoint hygrometer (NOAA-FPH), SAGE II, Halogen Occultation Experiment (HALOE), Microwave Limb Sounder (MLS)/Aura, and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) to model predictions based on troposphere-to-stratosphere transport from ERA-Interim, and temperatures from ERA-Interim, Modern Era Retrospective-Analysis (MERRA), Climate Forecast System Reanalysis (CFSR), Radiosonde Atmospheric Temperature Products for Assessing Climate (RATPAC), HadAT2, and RICHv1.5. All model predictions are dry biased. The interannual anomalies of the model predictions show periods of fairly regular oscillations, alternating with more quiescent periods and a few large-amplitude oscillations. They all agree well (correlation coefficients 0.9 and larger) with observations for higherfrequency variations (periods up to 2-3 years). Differences between SWV observations, and temperature data, respectively, render analysis of the model minus observation residual difficult. However, we find fairly well-defined periods of drifts in the residuals. For the 1980s, model predictions differ most, and only the calculation with ERA-Interim temperatures is roughly within observational uncertainties. All model predictions show a drying relative to HALOE in the 1990s, followed by a moistening in the early 2000s. Drifts to NOAA-FPH are similar (but stronger), whereas no drift is present against SAGE II. As a result, the model calculations have a less pronounced drop in SWV in 2000 than HALOE. From the mid-2000s onward, models and observations agree reasonably, and some differences can be traced to problems in the temperature data. These results indicate that both SWV and temperature data may still suffer from artifacts that need to be resolved in order to answer the question whether the large-scale flow and temperature field is sufficient to explain water entering the stratosphere.

The Limb Infrared Monitor of the Stratosphere (LIMS) measured polar stratospheric enhancements of NO2 mixing ratios due to energetic particle precipitation (EPP) in the Arctic winter of 1978-1979. Recently reprocessed LIMS data are compared to more recent measurements from the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) and the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS) to place the LIMS measurements in the context of current observations. The amount of NOx (NO + NO2) entering the stratosphere that has been created by EPP in the mesosphere and lower thermosphere (EPP-NOx) has been quantified for the 1978-1979 and 2002-2003 through 2008-2009 Arctic winters. The NO2 enhancements in the LIMS data are similar to those in MIPAS and ACE-FTS data in the Arctic winters of 2002-2003, 2004-2005, 2006-2007, and 2007-2008. The largest enhancement by far is in 2003-2004 (approximately 2.2 Gmol at 1500 K), which is attributed to a combination of elevated EPP and unusual dynamics that led to strong descent in the upper stratosphere/lower mesosphere in late winter. The enhancements in 2005-2006 and 2008-2009, during which large stratospheric NOx enhancements were caused by a dynamical situation similar to that in 2003 2004, are larger than in all the other years (except 2003-2004) at 3000 K. However, by 2000 K the enhancements in 2005-2006 (2008-2009) are on the same order of magnitude as (smaller than) all other years. These results highlight the importance of the timing of the descent in determining the potential of EPP-NOx for reaching the middle stratosphere.

Solar eruptions in early 2005 led substantial barrage of charged particles on the Earth's atmosphere during the January 16-21 period. Proton fluxes were greatly increased during these several days and led to the production ofHO(x)(H, OH, BO2)and NO(x)(N, NO, NO2), which then caused the destruction of ozone. We focus on the Northern polar region, where satellite measurements and simulations with the Whole Atmosphere Community Climate Model (WACCM3) showed large enhancements in mesospheric HO(x) and NO(x) constituents, and associated ozone reductions, due 10 these solar proton events (SPEs). The WACCM3 simulations show enhanced short-lived OH throughout the mesosphere in the 60-82.5degN latitude band due to the SPEs for most days in the Jan.16-2l,2005 period, in reasonable agreement with the Aura Microwave Limb Sounder (MLS) measurements. Mesospheric HO2 is also predicted to be increased by the SPEs, however, the modeled HO2 results are somewhat larger than the MLS measurements. These HO(x) enhancements led to huge predicted and MLS-measured ozone decreases of greater than 40% throughout most of the Northern polar mesosphere during the SPE period. Envisat Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) measurements of hydrogen peroxide (H2O2) show increases throughout the stratosphere with highest enhancements of about 60 ppt y in the lowermost mesosphere over the Jan. 16-18, 2005 period due to the solar protons. WACCM3 predictions indicate H2O2 enhancements over the same time period of more than twice that amount. Measurements of nitric acid (HNO3) by both MLS and MIPAS show an increase of about 1 ppbv above background levels in the upper stratosphere during January 16-29, 2005. WACCM3 simulations show only minuscule HNO3 changes in the upper stratosphere during this time period. However due to the small loss rates during winter, polar mesospheric enhancements of NO(x) are computed to be greater than 50 ppbv during the SPE period. Computed NO(x)increases, which were statistically significant at the 95% level, lasted about a month past the SPEs. The SCISAT-I Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) NO(x) measurements and MIPAS NO, measurements for the polar Northern Hemisphere are in reasonable agreement with these predictions. An extremely large ground level enhancement (GLE) occurred during the SPE period on January 20, 2005. We find that protons of energies 300 to 20,000 MeV, not normally included in our computations, led to enhanced lower stratospheric odd nitrogen concentrations of less than 0.1% as a result of this GLE.

We investigate the spatial and temporal distribution of hydrogen cyanide (HCN) in the upper troposphere through numerical simulations and comparison with observations from a space-based instrument. To perform the simulations, we used the Global Environmental Multiscale Air Quality model (GEM-AQ), which is based on the threedimensional Gobal multiscale model developed by the Meteorological Service of Canada for operational weather forecasting. The model was run for the period 2004-2006 on a 1.5deg x 1.5deg global grid with 28 hybrid vertical levels from the surface up to 10 hPa. Objective analysis data from the Canadian Meteorological Centre were used to update the meteorological fields every 24 h. Fire emission fluxes of gas species were generated by using year-specific inventories of carbon emissions with 8-day temporal resolution from the Global Fire Emission Database (GFED) version 2. The model output is compared with HCN profiles measured by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) instrument onboard the Canadian SCISAT-1 satellite. High values of up to a few ppbv are observed in the tropics in the Southern Hemisphere; the enhancement in HCN volume mixing ratios in the upper troposphere is most prominent in October. Low upper-tropospheric mixing ratios of less than 100 pptv are mostly recorded at middle and high latitudes in the Southern Hemisphere in May-July. Mixing ratios in Northern Hemisphere peak in the boreal summer. The amplitude of the seasonal variation is less pronounced than in the Southern Hemisphere. The comparison with the satellite data shows that in the upper troposphere GEM-AQ perform7s well globally for all seasons, except at northern hi gh and middle latitudes in surnmer, where the model has a large negative bias, and in the tropics in winter and spring, where it exhibits large positive bias. This may reflect inaccurate emissions or possible inaccuracies in the emission profile. The model is able to explain most of the observed variability in the upper troposphere HCN field, includin g the interannual variations in the observed mixing ratio. A complementary comparison with daily total columns of HCN from two middle latitude ground-based stations in Northern Japan for the same simulation period shows that the model captures the observed seasonal variation and also points to an underestimation of model emissions in the Northern Hemisphere in the summer. The estimated average global emission equals 1.3 Tg N/yr. The average atmospheric burden is 0.53 Tg N, and the corresponding lifetime is 4.9 months.

This work reports the first measurements of ethene (C2H4) distributions in the upper troposphere. These are obtained by retrieving vertical profiles from 5 to 20 km from infrared solar occultation spectra recorded in 2005 and 2006 by the Atmospheric Chemistry Experiment-Fourier Transform Spectrometer (ACE-FTS). Background volume mixin^ ratios (vmrs) ranging from a few to about 50 pptv (10(exp -1) are measured at the different altitudes, while for certain occultations, vmrs as high as 200 pptv are observed. Zonal distributions and vertically resolved latitudinal distributions are derived for the two year period analyzed, highlighting spatial - including a North-South gradient - as well as seasonal variations. We show the latter to be more pronounced at the highest latitudes, presumably as a result of less active photochemistry during winter. The observation of C2H4 enhancements in remote Arctic regions at high latitudes is consistent with the occurrence of fast transport processes of gaseous pollution from the continents leading to Arctic haze. Citation: Herbin, H., D. Hurtmans, L. Clarisse, S. Turquety, C. Clerbaux, C. P. Rinsland, C. Boone, P. F. Bernath, and P.-F. Colieur (2009), Distributions and seasonal variations of tropospheric ethene (C2H4) from Atmospheric Chemistry Experiment (ACE-FTS) solar occultation spectra

The Earth Observing System (EOS) Microwave Limb Sounder (MLS) aboard the Aura satellite has provided daily global HCl profiles since August 2004. We provide a characterization of the resolution, random and systematic uncertainties, and known issues for the version 2.2 MLS HCl data. The MLS sampling allows for comparisons with many (~1500 to more than 3000) closely matched profiles from the Halogen Occultation Experiment (HALOE) and Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS). These data sets provide HCl latitudinal distributions that are, overall, very similar to those from (coincident) MLS profiles, although there are some discrepancies in the upper stratosphere between the MLS and HALOE gradients. As found in previous work, MLS and ACE HCl profiles agree very well (within approximately 5%, on average), but the MLS HCl abundances are generally larger (by 10-20%) than HALOE HCl. The bias versus HALOE is unlikely to arise mostly from MLS, as a similar systematic bias (of order 15%) is not observed between average MLS and balloon-borne measurements of HCl, obtained over Fort Sumner, New Mexico, in 2004 and 2005. At the largest pressure (147 hPa) for MLS HCl, a high bias (approximately 0.2 ppbv) is apparent in analyses of low to midlatitude data versus in situ aircraft chemical ionization mass spectrometry (CIMS) HCl measurements from the Aura Validation Experiment (AVE) campaigns in 2004, 2005, and 2006; this bias is also observed in comparisons of MLS and aircraftHCl/O3 correlations. Good agreement between MLS and CIMS HCl is obtained at 100 to 68 hPa. The recommended pressure range for MLS HCl is from 100 to 0.15 hPa.

The quality of the version 2.2 (v2.2) middle atmosphere water vapor and nitrous oxide measurements from the Microwave Limb Sounder (MLS) on the Earth Observing System (EOS) Aura satellite is assessed. The impacts of the various sources of systematic error are estimated by a comprehensive set of retrieval simulations. Comparisons with correlative data sets from ground-based, balloon and satellite platforms operating in the UV/visible, infrared and microwave regions of the spectrum are performed. Precision estimates are also validated, and recommendations are given on the data usage. The v2.2 H2O data have been improved over v1.5 by providing higher vertical resolution in the lower stratosphere and better precision above the stratopause. The single-profile precision is ~0.2–0.3 ppmv (4–9%), and the vertical resolution is ~3–4 km in the stratosphere. The precision and vertical resolution become worse with increasing height above the stratopause. Over the pressure range 0.1–0.01 hPa the precision degrades from 0.4 to 1.1 ppmv (6–34%), and the vertical resolution degrades to ~12–16 km. The accuracy is estimated to be 0.2–0.5 ppmv (4–11%) for the pressure range 68–0.01 hPa. The scientifically useful range of the H2O data is from 316 to 0.002 hPa, although only the 82–0.002 hPa pressure range is validated here. Substantial improvement has been achieved in the v2.2 N2O data over v1.5 by reducing a significant low bias in the stratosphere and eliminating unrealistically high biased mixing ratios in the polar regions. The single-profile precision is ~13–25 ppbv (7–38%), the vertical resolution is ~4–6 km and the accuracy is estimated to be 3–70 ppbv (9–25%) for the pressure range 100–4.6 hPa. The scientifically useful range of the N2O data is from 100 to 1 hPa.

This paper describes the retrievals algorithm used to determine temperature and height from radiance measurements by the Microwave Limb Sounder on EOS Aura. MLS is a "limbscanning" instrument, meaning that it views the atmosphere along paths that do not intersect the surface - it actually looks forwards from the Aura satellite. This means that the temperature retrievals are for a "profile" of the atmosphere somewhat ahead of the satellite. Because of the need to view a finite sample of the atmosphere, the sample spans a box about 1.5km deep and several tens of kilometers in width; the optical characteristics of the atmosphere mean that the sample is representative of a tube about 200-300km long in the direction of view. The retrievals use temperature analyses from NASA's Goddard Earth Observing System, Version 5 (GEOS-5) data assimilation system as a priori states. The temperature retrievals are somewhat deperrde~zt on these a priori states, especially in the lower stratosphere. An important part of the validation of any new dataset involves comparison with other, independent datasets. A large part of this study is concerned with such comparisons, using a number of independent space-based measurements obtained using different techniques, and with meteorological analyses. The MLS temperature data are shown to have biases that vary with height, but also depend on the validation dataset. MLS data are apparently biased slightly cold relative to correlative data in the upper troposphere and slightly warm in the middle stratosphere. A warm MLS bias in the upper stratosphere may be due to a cold bias in GEOS-5 temperatures.

The Swan (d(sup 3)pi(sub g) - a(sup 3)pi(sub u)) system of the C2 molecule was produced in a jet-cooled corona excited supersonic expansion of helium using diazoacetonitrile as a percursor molecule. This spectrum was recorded using the McMath Fourier transform spectrometer of the National Solar Observatory at Kitt Peak. A total of nine bands with v prime = 0 to 3 and v prime prime = 0 to 4 in the range 16,570-22,760/cm were observed and rotationally analyzed. The C2 molecules in this source had a rotational temperature of only 90 K so that only the low-J lines were present in the spectrum. In some sense the low temperatures in the jet source simulate conditions in the interstellar medium. The Swan system of C2 was also produced in a composite wall hollow cathode made Al4C3/Cu, and the rotational structure of the 1-0, 2-1, 3-2, 0-0, and 1-1 bands were analyzed. The data obtained from both these spectra were fitted together along with some recently published line positions. The rotational constants, lambda doubling parameters and the vibrational constants were estimated from this global fit. Our work on jet-cooled C2 follows similar work on the violet and red systems of CN. A summary of this CN work is also presented. also presented.

Three electronic transitions of CaS are observed in the blue region of the spectrum. The vibrational bands in these transitions span thousands per cm owing to a large change in geometry. Approximately 1000/cm portion of the spectrum containing these bands is recorded at high resolution by dye laser excitation spectroscopy and analyzed. The states all have Omega = 1, and are tentatively labeled G 1Pi, F 1Pi, and f 3Pi 1. Spectroscopic constants are generated for all three upper states and for the X 1Sigma(+) state from a fit to 4340 individual lines. These constants are used to generate potential curves and Franck-Condon factors.