Rotational spectrum of cis–cis HOONO

The pure rotational spectrum of cis-cis peroxynitrous acid, HOONO, has been observed. Over 220 transitions, sampling states up to J(')=67 and K-a(')=31, have been fitted with an rms uncertainty of 48.4 kHz. The experimentally determined rotational constants agree well with ab initio values for the cis-cis conformer, a five-membered ring formed by intramolecular hydrogen bonding. The small, positive inertial defect Delta=0.075667(60) amu A(2) and lack of any observable torsional splittings in the spectrum indicate that cis-cis HOONO exists in a well-defined planar structure at room temperature

Rotational spectroscopy and dipole moment of cis-cis HOONO and DOONO

The rotational spectrum of cis-cis HOONO has been studied over a broad range of frequencies, 13–840 GHz, using pulsed beam Fourier-transform microwave spectroscopy and room-temperature flow cell submillimeter spectroscopy. The rotational spectrum of the deuterated isotopomer, cis-cis DOONO, has been studied over a subset of this range, 84–640 GHz. Improved spectroscopic constants have been determined for HOONO, and the DOONO spectrum is analyzed for the first time. Weak-field Stark effect measurements in the region of 84–110 GHz have been employed to determine the molecular dipole moments of cis-cis HOONO [µa=0.542(8) D,µb=0.918(15) D,µ=1.07(2) D] and DOONO [µa=0.517(9) D,µb=0.930(15) D,µ=1.06(2) D]. The quadrupole coupling tensor in the principal inertial axis system for the 14N nucleus has been determined to be chiaa=1.4907(25) MHz,chibb=–4.5990(59) MHz,chiab=3.17(147) MHz, and chicc=3.1082(59) MHz. Coordinates of the H atom in the center-of-mass frame have been determined with use of the Kraitchman equations, |aH|=0.516 Å and |bH|=1.171 Å. The inertial defects of HOONO and DOONO are consistent with a planar equilibrium structure with significant out-of-plane H atom torsional motion. Comparisons of the present results are made to ab initio calculations

Submillimeter Spectrum of Formic Acid

We have measured new submillimeter-wave data around 600 GHz and around 1.1 THz for the 13C isotopologue of formic acid and for the two deuterium isotopomers; in each case for both the trans and cis rotamer. For cis-DCOOH and cis-HCOOD in particular only data up to 50 GHz was previously available. For all species the quality and quantity of molecular parameters has been increased providing new measured frequencies and more precise and reliable frequencies in the range of existing and near-future submillimeter and far-infrared astronomical spectroscopy instruments such as Herschel, SOFIA and ALMA

A CMOS millimeter-wave transceiver embedded in a semi-confocal fabry-perot cavity

The extension of radio-frequency CMOS circuitry into millimeter wavelengths promises the extension of spectroscopic techniques in compact, power efficient systems. We are now exploring the use of CMOS millimeter devices for low-mass, low-power instrumentation capable of remote or in-situ detection of gas composition during space missions. We have chosen to develop a Flygare-Balle type spectrometer, with a semi-confocal Fabry-Perot cavity to amplify the pump power of a mm-wavelength CMOS transmitter that is directly coupled to the planar mirror of the cavity. Since the initial report last year describing the designs, we have built a pulsed transceiver system at 89-104 GHz inside a 5 cm base length cavity and demonstrated cavity finesse up to 3000, allowing for modes with 30 MHz bandwidth and a sufficient cavity amplification factor for mW class transmitters. System and component testing revealed that the power-amplifier design (embedded in the chip) was faulty and the transceiver peak power is only 10 microwatts, which is insufficient for molecular excitation on the timescale of the gas residence time within the beam. An improved power amplifier circuit has been designed and is currently under fabrication, meanwhile, we have also developed a tunable synthesizer (embedded in the same chip) that allows for tuning over the full bandwidth at increments of 10 MHz. The presentation will cover these capabilities, describing the system and component tests, as well as any new developments

MOLECULAR SPECTROSCOPY AT THE JET PROPULSION LABORATORY

Quantitative spectrometry is a primary source for determination of composition as well as physical properties of planetary atmospheres, including the Earth’s and exo-planetary atmospheres. NASAs charter to explore the universe, the solar system, and to observe Earth from space results in several different challenges for molecular spectroscopy, including: (1) a desire for comprehensive spectral databases; (2) extreme physical characterizations of bulk atmospheric gases; (3) characterization of transient molecules; (4) development of sensors for extraterrestrial deployment. Along with colleagues across the world, the molecular spectroscopy laboratory at NASAs Jet Propulsion Laboratory works towards these goals, providing both critical information for specific missions as well as general knowledge to support a broad community of planetary scientists, astronomers, and Earth scientists. This presentation will show examples in each challenging area with highlights for spectral characterization efforts to support the Herschel/HIFI and Cassini missions, high-pressure spectroscopy to support the OCO missions and exoplanet research, characterizations of radical and ion species, as well as the development of miniaturized cavity spectrometers that may enable molecular and enantiomeric specific detections \emph{in-situ}

Multispectrum analysis of the oxygen A-band

Retrievals of atmospheric composition from near-infrared measurements require measurements of airmass to better than the desired precision of the composition. The oxygen bands are obvious choices to quantify airmass since the mixing ratio of oxygen is fixed over the full range of atmospheric conditions. The OCO-2 mission is currently retrieving carbon dioxide concentration using the oxygen A-band for airmass normalization. The 0.25\% accuracy desired for the carbon dioxide concentration has pushed the required state-of-the-art for oxygen spectroscopy. To measure O$_2$ A-band cross-sections with such accuracy through the full range of atmospheric pressure requires a sophisticated line-shape model (Rautian or Speed-Dependent Voigt) with line mixing (LM) and collision induced absorption (CIA). Models of each of these phenomena exist, however, this work presents an integrated self-consistent model developed to ensure the best accuracy. It is also important to consider multiple sources of spectroscopic data for such a study in order to improve the dynamic range of the model and to minimize effects of instrumentation and associated systematic errors. The techniques of Fourier Transform Spectroscopy (FTS) and Cavity Ring-Down Spectroscopy (CRDS) allow complimentary information for such an analysis. We utilize multispectrum fitting software to generate a comprehensive new database with improved accuracy based on these datasets. The extensive information will be made available as a multi-dimensional cross-section (ABSCO) table and the parameterization will be offered for inclusion in the HITRANonline database

Laboratory Spectroscopy of CH(+) and Isotopic CH

The A1II - X1(Epsilon) electronic band of the CH(+) ion has been used as a probe of the physical and dynamical conditions of the ISM for 65 years. In spite of being one of the first molecular species observed in the ISM and the very large number of subsequent observations with large derived column densities, the pure rotational spectra of CH+ has remained elusive in both the laboratory and in the ISM as well. We report the first laboratory measurement of the pure rotation of the CH(+) ion and discuss the detection of CH-13(+) in the ISM. Also reported are the somewhat unexpected chemical conditions that resulted in laboratory production

POLAR RADIANT ENERGY IN THE FAR-INFRARED EXPERIMENT (PREFIRE)

\begin{wrapfigure}{r}{0pt} \includegraphics*[scale=0.15]{energy_balance_x.eps} \end{wrapfigure} Much of the Far-infrared radiation (FIR) emitted by the earth surface is trapped primarily by the insulating greenhouse effect. At the poles, the greenhouse effect is minimized by the nominal cold and dry atmospheric state. This is how a significant amount of absorbed solar energy is vented back to space, acting like a thermostat. Under these conditions, the effects of surface emissivity become disproportionately large and have a significant impact on the radiative balance. Earth system models have consistently under-estimated the rapid warming occurring in the Arctic, perhaps due to poor assumptions about the nature of far-infrared spectral emissions. The Polar Radiant Energy in the Far-InfraRed Experiment (PREFIRE) is a NASA Earth Ventures mission, currently in formulation, that would test the hypothesis that time-varying errors in FIR surface emissivity and atmospheric greenhouse effects bias the modeled energy balance that under-estimates Arctic warming. This presentation covers the processes involved in the energy balance, and how spectrally resolved measurements provide the means to extract critical information. We also discuss the instrument difficulties associated with remote measurements across the far-infrared, emphasizing the differing challenges associated with earth science vs. astrophysics. Finally, we provide an overview of the planned PREFIRE mission and how it would address these challenges

IMPLEMENTATION OF CMOS MILLIMETER-WAVE DEVICES FOR ROTATIONAL SPECTROSCOPY

The extension of radio-frequency CMOS circuitry into millimeter wavelengths promises the extension of spectroscopic techniques in compact, power efficient systems. We are now exploring the use of CMOS millimeter devices for low-mass, low-power instrumentation capable of remote or in-situ detection of gas composition during space missions. This effort focuses on the development of a semi-confocal Fabry-Perot cavity with mm-wavelength CMOS transmitter and receiver attached directly to a cavity coupler. Placement of the devices within the cavity structure bypasses problems encountered with signal injection and extraction in traditional cavity designs and simultaneously takes full advantage of the miniaturized form of the CMOS hardware. The presentation will provide an overview of the project and details of the accomplishments thus far, including the development and testing of a pulse modulated 83-98 GHz transmitter

HIGH PRESSURE OXYGEN A-BAND SPECTRA

Composition measurements from remote sensing platforms require knowledge of air mass to better than the desired precision of the composition. Oxygen spectra allow determination of air mass since the mixing ratio of oxygen is fixed. The OCO-2 mission is currently retrieving carbon dioxide concentration using the oxygen A-band for air mass normalization. The 0.25% accuracy desired for the carbon dioxide concentration has pushed the state-of-the-art for oxygen spectroscopy. To produce atmospheric pressure A-band cross-sections with this accuracy requires a sophisticated line-shape model (Galatry or Speed-Dependent) with line mixing (LM) and collision induced absorption (CIA). Models of each of these phenomena exist, but an integrated self-consistent model must be developed to ensure accuracy. This presentation will describe the ongoing effort to parameterize these phenomena on a representative data set created from complementary experimental techniques. The techniques include Fourier transform spectroscopy (FTS), photo-acoustic spectroscopy (PAS) and cavity ring-down spectroscopy (CRDS). CRDS data allow long-pathlength measurements with absolute intensities, providing lineshape information as well as LM and CIA, however the subtleties of the lineshape are diminished in the saturated line-centers. Conversely, the short paths and large dynamic range of the PAS data allow the full lineshape to be discerned, but with an arbitrary intensity axis. Finally, the FTS data provides intermediate paths and consistency across a broad pressure range. These spectra are all modeled with the Labfit software using first the spectral line database HITRAN, and then model values are adjusted and fitted for better agreement with the data