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Rotational spectroscopy of atmospheric molecules has long been a hallmark of laboratory and field studies at the Jet Propulsion Laboratory. in addition to maintenance of the millimeter and submillimeter spectral line catalog, the laboratory has actively purued the challenging laboratory tasks of quantitative linewidth measurements and transient species identification.
Evidence is presented that microwave rotational spectroscopy can be developed for use in air pollution monitoring, with the employment of a diode-cavity spectrometer capable of detecting small concentrations of NO2, SO2, H2CO, and HN3 gas with very high specificity. The theory behind the technique is discussed, together with its application and experimental results.
Environmental monitoring, atmospheric remote sensing and astrophysical studies promoted by NASA require a strong basis of spectroscopic information. The rotational spectroscopy capabilities at NASAs Jet Propulsion Laboratory (JPL) are currently maintained for the measurement of key mission priorities that enable modeling and retrieval of geophysical data from the atmosphere as well as validation of the space-borne instruments in the Earth Observing System, particularly the Microwave Limb Sounder. Rotational spectra are measured using a variety of spectroscopic techniques including pulsed-beam Fourier transform microwave spectroscopy (at CalTech); millimeter wavelength Stark spectroscopy; millimeter, submillimeter and THz FM spectroscopy; laser sideband spectroscopy and Fourier Transform far-infrared spectroscopy. Remote measurements of atmospheric rotational spectra are made using two limb-sounder instruments in the submillimeter and THz. Recent advances in the direct synthesis of THz radiation that enable more efficient laboratory science will be presented. Software for comprehensive and systematic study of different molecular systems is maintained at JPL, the software is freely available via http://spec.jpl.nasa.gov and is used by our group to create and sustain the JPL spectral line catalog also available online.
An attempt was made to present substantial evidence that microwave rotational spectroscopy can be developed for use in air pollution monitoring. Work with the diode-cavity spectrometer shows it to be capable to detecting small concentrations on NO2, SO2, H2,CO, and NH3 gas with very high specificity.
A variety of organic compounds has been detected in comets, meteorites, and the cold gas enveloping infant stars. These compounds display a range of complexity and include so-called complex organic molecules that may have astrobiological implications. Laboratory studies of photolyzed and nonirradiated interstellar, planetary, and cometary ices have demonstrated many astrochemical formation routes and require sensitive analytical techniques to identify the composition of ice and gas products formed. The unique identification of organics can be challenging and often requires structure-specific techniques to identify structural isomers, conformers, and isotopologues. We present the approaches used in SubLIME, the Sublimation of Laboratory Ices Millimeter/submillimeter Experiment, which uses the structure-specificity of rotational spectroscopy to identify the composition and abundances of sublimated products of UV-photolyzed ice samples. Ices are formed and photolyzed at low temperature (~10 K) and slowly heated to 300 K to sublimate the volatile products. The gas mixture is then investigated with millimeter/submillimeter spectroscopy, and the resulting spectra compared to observational spectra collected with submillimeter/far-IR telescopes. We present the experimental set-up and results of UV-photolyzed interstellar ice analogues containing water (H O) and carbon monoxide (CO). Formation routes for identified molecules are proposed for follow-up experimental and theoretical investigations.
Remote sensing of rotational transitions in the Earth's atmosphere has become an important method for the retrieval of geophysical temperatures, pressures and chemical composition profiles that requires accurate spectral information. This paper highlights the current status of rotational data that are useful for atmospheric measurements, with a discussion of the types the rotational lineshape measurements that are not generally available in either online repository.
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The region of planetary atmospheres upward of 1 millimeter is considered. The applications of this region, how microwave, millimeter, and submillimeter spectra (the so called rotational spectra) can fruitfully interact with infrared spectral measurements are described. Both the rotational bands and vibrational bands of molecules are considered. A typical rotational absorption coefficient for a linear molecule in a low J state with a dipole moment of about one Debye is plotted and evaluated. A vibrational case was chosen similarly: the transition dipole moment used for the vibrational case is typical of CO at the peak of its rotational distribution. Information on high altitude parameters that often cannot be obtained from higher frequency spectra, which can be provided by rotational spectra is discussed.
Comprehensive information on the composition and dynamics of the varied planetary atmospheres is summarized. New observations resulted in new demands for supporting laboratory studies. Spectra observed from spacecraft used to interpret planetary atmospheric structure measurements, to aid in greenhouse and cloud physics calculations, and to plan future experiments are discussed. Current findings and new ideas of physicists, chemists, and planetry astronomers relating to the knowledge of the structure of things large and small, of planets and of molecules are summarized.
The planetary atmospheres are investigated for their chemical composition. Hydrogen, methane, ethylene, acetylene, and ethane were studied. Various spectroscopic investigations were made.
The technique of Stark modulation spectroscopy for unraveling and assigning rotationally resolved dense molecular spectra has been employed using a tunable diode laser (TDL) source. Doppler-limited absorption and Stark modulation spectra of the HNO3 7.5-micron band near the 1326/cm band origin are presented with preliminary values of the excited-state rovibrational constants derived from both TDL and Bomem Fourier transform IR spectra.
We discuss past and recent progress in our long-term laboratory program concerning the submillimeter-wave rotational spectroscopy of known and likely interstellar molecules, especially those associated with regions of high-mass star formation. Our program on the use of spectroscopy to study rotationally inelastic collisions of interstellar interest is also briefly mentioned.
High resolution rotational spectroscopy has long been central to remote sensing techniques in atmospheric sciences and astronomy. As such, laboratory measurements must supply the required data to make direct interpretation of data for instruments which sense atmospheres using rotational spectra. Spectral measurements in the microwave and far infrared regions are also very powerful tools when combined with infrared measurements for characterizing the rotational structure of vibrational spectra. In the past decade new techniques were developed which have pushed high resolution spectroscopy into the wavelength region between 25 micrometers and 2 mm. Techniques to be described include: (1) harmonic generation of microwave sources, (2) infrared laser difference frequency generation, (3) laser sideband generation, and (4) ultrahigh resolution interferometers.
Molecule specific astronomical observations rely on precisely determined laboratory molecular data for interpretation. The Herschel Heterodyne Instrument for Far Infrared, a suite of SOFIA instruments, and ALMA are each well placed to expose the limitations of available molecular physics data and spectral line catalogs. Herschel and SOFIA will observe in high spectral resolution over the entire far infrared range. Accurate data to previously unimagined frequencies including infrared ro-vibrational and ro-torsional bands will be required for interpretation of the observations. Planned ALMA observations with a very small beam will reveal weaker emission features requiring accurate knowledge of higher quantum numbers and additional vibrational states. Historically, laboratory spectroscopy has been at the front of submillimeter technology development, but now astronomical receivers have an enormous capability advantage. Additionally, rotational spectroscopy is a relatively mature field attracting little interest from students and funding agencies. Molecular database maintenance is tedious and difficult to justify as research. This severely limits funding opportunities even though data bases require the same level of expertise as research. We report the application of some relatively new receiver technology into a simple solid state THz spectrometer that has the performance required to collect the laboratory data required by astronomical observations. Further detail on the lack of preparation for upcoming missions by the JPL spectral line catalog is given.
A new laboratory technique has been developed that utilizes gas-phase, direct-absorption millimeter and submillimeter spectroscopy to detect and identify desorbed species from interstellar and cometary ice analogs. Rotational spectroscopy is a powerful structure-specific technique for detecting isomers and other species possessing the same mass that are indistinguishable with mass spectrometry. Furthermore, the resultant laboratory spectra are directly comparable to observational data from far-infrared and millimeter telescopes. Here we present the proof-of-concept measurements of the detection of thermally desorbed H2O, D2O, and CH3OH originating in a solid film created at low temperature (~12 K). The surface binding energy of H2O is reported and compared to results from traditional techniques, including mass spectrometry and quartz-crystal microbalance measurements of mass loss. Lastly, we demonstrate that this technique is capable of deriving thermodynamic values including the sublimation enthalpy and entropy of H2O.
The detection of molecules in astrophysical environments almost always requires remote sensing. While radioastronomical observation and associated rotational spectroscopy are powerful astronomical tools, infrared spectral analysis provides a unique means of examining the observable universe, especially for molecules where permanent dipole moments are small or even non-existent. The molecular vibrations of small molecules are now able to be modeled via quantum chemistry and electronic structure theory conjoined to vibrational analysis to within spectroscopic accuracy in many cases. This chapter will showcase this success and build upon it to show how such advances are now being leveraged to describe molecular vibrations for molecules containing dozens of atoms, electronically excited states, "hot bands," exoplanetary atmospheric opacity data, and even emission of polycyclic aromatic hydrocarbons. All of these are required to prune the interstellar spectral garden of its "weeds" in search of "flowers" that will provide the necessary fingerprints for astronomers to be able to probe the heavens for its past, present, and future secrets.