489 research outputs found
Hot methane line lists for exoplanet and brown dwarf atmospheres
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
referenc
Balloon-borne radiometer measurement of Northern Hemisphere mid-latitude stratospheric HNO3 profiles spanning 12 years
Low-resolution atmospheric thermal emission spectra collected by balloon-borne radiometers over the time span of 1990–2002 are used to retrieve vertical profiles of HNO3, CFC-11 and CFC-12 volume mixing ratios between approximately 10 and 35 km altitude. All of the data analyzed have been collected from launches from a Northern Hemisphere mid-latitude site, during late summer, when stratospheric dynamic variability is at a minimum. The retrieval technique incorporates detailed forward modeling of the instrument and the radiative properties of the atmosphere, and obtains a best fit between modeled and measured spectra through a combination of onion-peeling and global optimization steps. The retrieved HNO3 profiles are consistent over the 12-year period, and are consistent with recent measurements by the Atmospheric Chemistry Experiment-Fourier transform spectrometer satellite instrument. This suggests that, to within the errors of the 1990 measurements, there has been no significant change in the HNO3 summer mid-latitude profile
Spectroscopic Constants, Abundances, and Opacities of the TiH Molecule
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
0.52 \mic, 0.94 \mic, and in the 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 Journa
Note: Improved line strengths of rovibrational and rotational transitions within the X3Σ− ground state of NH
Recently, a line list including positions and transition strengths was published for the NH X3Σ− rovibrational and rotational transitions. The calculation of the transition strengths requires a conversion of transition matrix elements from Hund’s case (b) to (a). The method of this conversion has recently been improved during other work on the OH X2Πrovibrational transitions, by removing an approximation that was present previously. The adjusted method has been applied to the NH line list, resulting in more accurate transition strengths. An updated line list is presented that contains all possible transitions with v′ and v″ up to 6, and J up to between 25 and 44, depending on the band
Line Strengths of Rovibrational and Rotational Transitions in the X Ground State of OH
A new line list including positions and absolute intensities (in the form of
Einstein 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 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 values, and 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.doc
Accurate <i>ab initio</i> ro-vibronic spectroscopy of the X<sup>2</sup>∏ CCN radical using explicitly correlated methods
Explicitly correlated CCSD(T)-F12b calculations have been carried out with systematic sequences of correlation consistent basis sets to determine accurate near-equilibrium potential energy surfaces for the X<sup>2</sup>∏ and a<sup>4</sup>Σ<sup>−</sup> electronic states of the CCN radical. After including contributions due to core correlation, scalar relativity, and higher order electron correlation effects, the latter utilizing large-scale multireference configuration interaction calculations, the resulting surfaces were employed in variational calculations of the ro-vibronic spectra. These calculations also included the use of accurate spin-orbit and dipole moment matrix elements. The resulting ro-vibronic transition energies, including the Renner-Teller sub-bands involving the bending mode, agree with the available experimental data to within 3 cm<sup>−1</sup> in all cases. Full sets of spectroscopic constants are reported using the usual second-order perturbation theory expressions. Integrated absorption intensities are given for a number of selected vibronic band origins. A computational procedure similar to that used in the determination of the potential energy functions was also utilized to predict the formation enthalpy of CCN, ΔH<sub>f</sub>(0K) = 161.7 ± 0.5 kcal/mol
CH in stellar atmospheres: an extensive linelist
The advent of high-resolution spectrographs and detailed stellar atmosphere
modelling has strengthened the need for accurate molecular data.
Carbon-enhanced metal-poor (CEMP) stars spectra are interesting objects with
which to study transitions from the CH molecule. We combine programs for
spectral analysis of molecules and stellar-radiative transfer codes to build an
extensive CH linelist, including predissociation broadening as well as newly
identified levels. We show examples of strong predissociation CH lines in CEMP
stars, and we stress the important role played by the CH features in the
Bond-Neff feature depressing the spectra of barium stars by as much as 0.2
magnitudes in the 3000 -- 5500 \AA\ range. Because of the extreme
thermodynamic conditions prevailing in stellar atmospheres (compared to the
laboratory), molecular transitions with high energy levels can be observed.
Stellar spectra can thus be used to constrain and improve molecular data.Comment: 33pages, 15 figures, accepted in A&A external data available at
http://www.astro.ulb.ac.be/~spectrotools
Rubidium Rydberg macrodimers
We explore long-range interactions between two atoms excited into high
principal quantum number n Rydberg states, and present calculated potential
energy surfaces (PES) for various symmetries of doubly excited ns and np
rubidium atoms. We show that the PES for these symmetries exhibit deep (~GHz)
potential wells, which can support very extended (~micrometers) bound
vibrational states (macrodimers). We present n-scaling relations for both the
depth De of the wells and the equilibrium separations Re of these macrodimers,
and explore their response to small electric fields and stability with respect
to predissociation. Finally, we present a scheme to form and study these
macrodimers via photoassociation, and show how one can probe the various
\ell-character of the potential wells
Global Stratospheric Measurements of the Isotopologues of Methane From the Atmospheric Chemistry Experiment Fourier Transform Spectrometer
This paper presents an analysis of observations of methane and its two major isotopologues, CH3D and 13CH4, from the Atmospheric Chemistry Experiment (ACE) satellite between 2004 and 2013. Additionally, atmospheric methane chemistry is modeled using the Whole Atmospheric Community Climate Model (WACCM). ACE retrievals of methane extend from 6 km for all isotopologues to 75 km for 12CH4, 35 km for CH3D, and 50 km for 13CH4. While total methane concentrations retrieved from ACE agree well with the model, values of δD-CH4 and δ13C-CH4 show a bias toward higher δ compared to the model and balloon-based measurements. Errors in spectroscopic constants used during the retrieval process are the primary source of this disagreement. Calibrating δD and δ13C from ACE using WACCM in the troposphere gives improved agreement in δD in the stratosphere with the balloon measurements, but values of δ13C still disagree. A model analysis of methane\u27s atmospheric sinks is also performed
Stratospheric Lifetimes of CFC-12, CCl4, CH4, CH3CL and N20 from Measurements Made By The Atmospheric Chemistry Experiment-Fourier Transform Spectrometer
Long lived halogen-containing compounds are important atmospheric constituents since they can act both as a source of chlorine radicals, which go on to catalyse ozone loss, and as powerful greenhouse gases. The long-term impact of these species on the ozone layer is dependent on their stratospheric lifetimes. Using observations from the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) we present calculations of the stratospheric lifetimes of CFC-12, CCl4, CH4, CH3Cl and N2O. The lifetimes were calculated using the slope of the tracer-tracer correlation of these species with CFC-11 at the tropopause. The correlation slopes were corrected for the changing atmospheric concentrations of each species based on age of air and CFC-11 measurements from samples taken aboard the Geophysica aircraft - along with the effective linear trend of the volume mixing ratio (VMR) from tropical ground based AGAGE (Advanced Global Atmospheric Gases Experiment) sites. Stratospheric lifetimes were calculated using a CFC-11 lifetime of 45 yr. These calculations produced values of 113 + (-) 26 (18) yr (CFC-12), 35 + (-) 11 (7) yr (CCl4), 69 + (-) 65 (23) yr (CH3Cl), 123 + (-) 53 (28) yr (N2O) and 195 + (-) 75 (42) yr (CH4). The errors on these values are the weighted 1 sigma non-systematic errors. Systematic errors were estimated by recalculating lifetimes using VMRs which had been modified to reflect differences between ACE-FTS retrieved VMRs and those from other instruments. The results of these calculations, including systematic errors, were as follows: 113 + (-) 32 (20) for CFC-12, 123 + (-) 83 (35) for N2O, 195 + (-) 139 (57) for CH4, 35 + (-) 14 (8) for CCl4 and 69 + (-) 2119 (34) yr for CH3Cl. For CH3Cl & CH4 this represents the first calculation of the stratospheric lifetime using data from a space based instrument
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