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High-resolution absorption spectroscopy of room-temperature and jet-cooled ammonia between 59,000 and 93,000 cm -1

Here, we present new high-resolution photoabsorption spectra of ammonia spanning the region between 59,000 cm -1 and 93,000 cm -1 that were recorded by using the Fourier Transform Spectrometer at the Synchrotron SOLEIL. This region extends from just above the Franck-Condon envelope for the $\tilde{A}$ 1 $A$ 2 " ← $\tilde{X}$ 1 $A$ 1 ' transition to well above the NH 3 + $\tilde{X}$ + 2 $A$ 2 " ionization threshold. The spectra were recorded at a measured resolution of 0.23 cm -1 in both a room-temperature cell (293 K) and in a slit-jet supersonic expansion (~70 K). The absolute photoabsorption cross section with an uncertainty of ±5% is also reported for the room-temperature spectrum. The present resolution is a factor of 10 – 100 times higher than in other recently reported broad band spectra of ammonia, and many of the observed bands show partially resolved rotational structure. We have attempted to assign this structure for a number of these bands. The oscillator strengths extracted from the data are in good agreement with previous measurements but, in the case of structured bands, the present higher resolution measurements return higher peak absorption cross sections, that increase further when the sample is cooled. The present higher resolution spectra suggest that a number of previous vibronic band assignments that were based on quantum defect considerations may require some revision. Finally, we discuss the substantial differences between the photoabsorption and photoionization data just above the first ionization threshold.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

High-resolution Infrared Spectroscopy of Hot Molecular Gas in AFGL 2591 and AFGL 2136: Accretion in the Inner Regions of Disks around Massive Young Stellar Objects

We have performed a high-resolution 4–13 μm spectral survey of the hot molecular gas associated with the massive protostars AFGL 2591 and AFGL 2136, utilizing the Echelon Cross Echelle Spectrograph (EXES) on board the Stratospheric Observatory for Infrared Astronomy, and the iSHELL instrument and Texas EchelonCross Echelle Spectrograph (TEXES) on the NASA Infrared Telescope Facility (IRTF). Here we present the results of this survey with analysis of CO, HCN, C2H2, NH3, and CS, deriving the physical conditions for each species. Also from the IRTF, iSHELL data at 3 μm for AFGL 2591are presented that show HCN and C2H2 in emission. In the EXES and TEXES data, all species are detected in absorption, and temperatures and abundances are found to be high (600 K and 10−6, respectively). Differences of up to an order of magnitude in the abundances of transitions that trace the same ground-state level are measured for HCN and C2H2. The mid-infrared continuum is known to originate in a disk, hence we attribute the infrared absorption to arise in the photosphere of the disk. As absorption lines require an outwardly decreasing temperature gradient, we conclude that the disk is heated in the midplane by viscous heating due to accretion. We attribute the near-IR emission lines to scattering by molecules in the upper layers of the disk photosphere. The absorption lines trace the disk properties at 50 au where high-temperature gasphase chemistry is taking place. Abundances are consistent with chemical models of the inner disk of Herbig disks.

Andrew Barr↗

Mass loss from red giants - Infrared spectroscopy

A discussion is presented of IR spectroscopy, particularly high-resolution spectroscopy in the approximately 1-20 micron band, as it impacts the study of circumstellar envelopes. The molecular bands within this region contain an enormous amount of information, especially when observed with sufficient resolution to obtain kinematic information. In a single spectrum, it is possible to resolve lines from up to 50 different rotational/vibrational levels of a given molecule and to detect several different isotopic variants. When high resolution techniques are combined with mapping techniques and/or time sequence observations of variable stars, the resulting information can paint a very detailed picture of the mass-loss phenomenon. To date, near-IR observations have been made of 20 molecular species. CO is the most widely observed molecule and useful information has been gleaned from the observed rotational excitation, kinematics, time variability and spatial structure of its lines. Examples of different observing techniques are discussed in the following sections.

Wannier, P. G.↗

High-resolution infrared spectroscopy of jet cooled CH 2 Br radicals: The symmetric CH stretch manifold and absence of nuclear spin cooling

Direct laser absorption of a slit supersonic discharge expansion provides the first high-resolution spectroscopic results on the symmetric CH stretch excitation (ν 1 ) of the bromomethyl (CH 2 Br) radical in the ground electronic state. Narrowband (<1 MHz) mid-infrared radiation is produced by difference-frequency generation of two visible laser beams, with the open shell halohydrocarbon radical generated by electron dissociative attachment of CH 2 Br 2 in a discharge and rapidly cooled to T rot = 18 ± 1 K in the subsequent slit-jet supersonic expansion. A rovibrational structure in the radical spectrum is fully resolved, as well as additional splittings due to spin-rotation effects and 79 Br/ 81 Br isotopologues in natural abundance. Spectroscopic constants and band origins are determined by fitting the transition frequencies to a non-rigid Watson Hamiltonian, yielding results consistent with a vibrationally averaged planar radical and an unpaired electron in the out-of-plane p π orbital. Additionally, extensive satellite band structure from a vibrational hot band is observed and analyzed. The hot band data is compared to CFOUR/VPT2 (CCSD(T)cc-pVQZ) ab initio anharmonic predictions of the vibration rotation alpha matrix, which permits unambiguous assignment to CH 2 symmetric-stretch excitation built on the singly excited CH 2 out-of-plane bending mode (ν 1 + ν 4 ← ν 4 ). Longitudinal cooling of the Doppler width in the slit-jet expansion geometry also reveals partially resolved hyperfine structure on transitions out of the lowest angular momentum states in excellent agreement with predictions based on microwave studies. High level ab initio MOLPRO calculations [CCSD(T)-f12b/VnZ-f12 (n = 3, 4, CBS)] are also performed with explicitly correlated f12 electron methods for the out-of-plane CH 2 bending mode over the halogen series CH 2 X (X = F, Cl, Br, I), which clearly reveals a non-planar geometry for X = F (with a ΔE ≈ 0.3 kcal/mol barrier) and yet planar equilibrium geometries for X = Cl, Br, and I. Finally, a detailed Boltzmann analysis of the transition intensities provides support for negligible collisional equilibration of the entangled H atom nuclear spin states on the few hundred microsecond time scale and high collision densities of a slit supersonic expansion.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

New RHESSI Results on Particle Acceleration and Energy Release in Solar Flares

The primary scientific objective of NASA RHESSI mission (launched February 2002) is to investigate the physics of particle acceleration and energy release in solar flares, through imaging and spectroscopy of X-ray gamma-ray continuum and gamma-ray lines emitted by accelerated electrons and ions, respectively. Here I summarize the new solar observations, including the first hard X-ray imaging spectroscopy, the first high resolution spectroscopy of solar gamma ray lines, the first imaging of solar gamma ray lines and continuum, and the highest sensitivity hard X-ray observations of microflares and type III solar radio bursts.

Lin, R. P.↗

High-resolution Compton spectroscopy using x-ray microcalorimeters

X-ray Compton spectroscopy is one of the few direct probes of the electron momentum distribution of bulk materials in ambient and operando environments. Herein, we report high-resolution inelastic x-ray scattering experiments with high momentum and energy transfer performed at a storage-ring-based high-energy x-ray light source facility using an x-ray transition-edge sensor (TES) microcalorimeter detector. The performance was compared with a silicon drift detector (SDD), an energy-resolving semiconductor detector, and Compton profiles were measured for lithium and cobalt oxide powders relevant to lithium-ion battery research. Spectroscopic analysis of the measured Compton profiles demonstrates the high-sensitivity to the low- Z elements and oxidation states. The line shape analysis of the measured Compton profiles in comparison with computed Hartree–Fock profiles is usually limited by the resolution of the semiconductor detector. We have characterized an x-ray TES microcalorimeter detector for high-resolution Compton scattering experiments using a bending magnet source at the Advanced Photon Source with a double crystal monochromator, providing monochromatic photon energies near 27.5 keV. The momentum resolution below 0.16 atomic units (a.u.) was measured, yielding an improvement of more than a factor of 7 over a state-of-the-art SDD for the same scattering geometry. Furthermore, the lineshapes of narrow valence and broad core electron profiles of sealed lithium metal were clearly resolved using an x-ray TES compared to smeared and broadened lineshapes observed when using the SDD. High-resolution Compton scattering using the energy-resolving area detector shown here presents new opportunities for spatial imaging of electron momentum distributions for a wide class of materials with applications ranging from electrochemistry to condensed matter physics.

47 OTHER INSTRUMENTATION↗

High-resolution atmospheric spectroscopy using a diode laser heterodyne spectrometer

A tunable-diode-laser radiometer with a spectral resolution of 0.007/cm was used to obtain IR solar absorption spectra in the 9.1-11.1 micron region. Spectra exhibiting absorption by HNO3, CO2, O3, and H2O were obtained in a piecewise manner using emission modes from a single Pb-salt laser local oscillator. The measured spectra were compared to synthetic atmospheric spectra calculated using a line-by-line model. The results demonstrate that high-resolution IR solar absorption spectroscopy and atmospheric extinction measurements can be routinely performed over wide spectral regions using semiconductor lasers.

Hoell, J. M., Jr.↗

Measuring molecular flows with high-resolution stimulated Raman spectroscopy

It is proposed to use high-resolution stimulated Raman spectroscopy to directly measure high-speed molecular flow velocities in wind tunnels and in combustive chambers. A feasibility study indicates that flow speeds from Mach 0.04 up may be measured with the proposed method using available laser systems. It is pointed out that the success of the proposed technique will make it possible to measure all interesting flow parameters, i.e., species concentration, temperature, and velocity, in a time of less than 1 microsecond at a repetition rate of 10,000/s using a single experimental arrangement.

She, C. Y.↗

High Resolution Emission Spectroscopy of the Alpha Pi-1 - Chi Sigma-1(+) Fourth Positive Band System of CO from Electron Impact

We report electron-impact induced fluorescence spectra [300 mA full width at half maximum (FWHM)] of CO for 20 and 100 eV impact energies of the spectral region of 1300 to 2050 A and high resolution spectra (FWHM) of the v'=5 to v"=l and the v'=3 to v"=O bands showing that the rotational structure of the band system are modeled accurately. The excitation function of the (0,1) band (1597 A) was measured from electron impact in the energy range from threshold to 750 eV and placed on an absolute scale from modem calibration standards.

Beegle, Luther W.↗

The Compositional Evolution of C/2012 S1 (ISON) from Ground-Based High-Resolution Infrared Spectroscopy as Part of a Worldwide Observing Campaign

Volatile production rates, relative abundances, rotational temperatures, and spatial distributions in the coma were measured in C/2012 S1 (ISON) using long-slit high-dispersion (lambda/delta lambda approximately 2.5 times 10 (sup 4)) infrared spectroscopy as part of a worldwide observing campaign. Spectra were obtained on Universal Time 2013 October 26 and 28 with NIRSPEC (Near Infrared Spectrometer) at the W.M. Keck Observatory, and Universal Time 2013 November 19 and 20 with CSHELL (Cryogenic Echelle Spectrograph) at the NASA IRTF (Infrared Telescope Facility). H2O was detected on all dates, with production rates increasing markedly from (8.7 plus or minus 1.5) times 10 (sup 27) molecules per second on October 26 (Heliocentric Distance = 1.12 Astronomical Units) to (3.7 plus or minus 0.4) times 10 (sup 29) molecules per second on November 20 (Heliocentric Distance = 0.43 Astronomical Units). Short-term variability of H2O production is also seen as observations on November 19 show an increase in H2O production rate of nearly a factor of two over a period of about 6 hours. C2H6, CH3OH and CH4 abundances in ISON (International Scientific Optical Network) are slightly depleted relative to H2O when compared to mean values for comets measured at infrared wavelengths. On the November dates, C2H2, HCN and OCS abundances relative to H2O appear to be within the range of mean values, whereas H2CO and NH3 were significantly enhanced. There is evidence that the abundances with respect to H2O increased for some species but not others between October 28 (Heliocentric Distance = 1.07 Astronomical Units) and November 19 (Heliocentric Distance = 0.46 Astronomical Units). The high mixing ratios of H2CO to CH3OH and C2H2 to C2H6 on November 19, and changes in the mixing ratios of some species with respect to H2O between October 28 to November 19, indicates compositional changes that may be the result of a transition from sampling radiation-processed outer layers in this dynamically new comet to sampling more pristine natal material as the outer processed layer was increasingly eroded and the thermal wave propagated into the nucleus as the comet approached perihelion for the first time. On November 19 and 20, the spatial distribution for dust appears asymmetric and enhanced in the antisolar direction, whereas spatial distributions for volatiles (excepting CN) appear symmetric with their peaks slightly offset in the sunward direction compared to the dust. Spatial distributions for H2O, HCN, C2H6, C2H2, and H2CO on November 19 show no definitive evidence for significant contributions from extended sources; however, broader spatial distributions for NH3 and OCS may be consistent with extended sources for these species. Abundances of HCN and C2H2 on November 19 and 20 are insufficient to account for reported abundances of CN and C2 in ISON near this time. Differences in HCN and CN spatial distributions are also consistent with HCN as only a minor source of CN in ISON on November 19 as the spatial distribution of CN in the coma suggests a dominant distributed source that is correlated with dust and not volatile release. The spatial distributions for NH3 and NH2 are similar, suggesting that NH3 is the primary source of NH2 with no evidence of a significant dust source of NH2; however, the higher production rates derived for NH3 compared to NH2 on November 19 and 20 remain unexplained. This suggests a more complete analysis that treats NH2 as a distributed source and accounts for its emission mechanism is needed for future work.

Russo, N. Dello↗

High resolution infrared spectroscopy of planetary molecules using diode lasers and Fourier transform spectrometers

Modern observations of infrared molecular lines in planets are performed at spectral resolutions which are as high as those available in the laboratory. Analysis of such data requires laboratory measurements at the highest possible resolution, which also yield accurate line positions and intensities. For planetary purposes the spectrometer must be coupled to sample cells which can be reduced in temperature and varied in pressure. An approach which produces the full range of required molecular line parameters uses a combination of tunable diode lasers and Fourier transform spectrometers (FTS). The FTS provides board spectral coverage and good calibration accuracy, while the diode laser can be used to study those regions which are not resolved by the FTS.

Jennings, Donald E.↗

High-Resolution Photoelectron Spectroscopy of NO3 – Vibrationally Excited Along Its ν3 Mode

The nitrate (NO3) radical has long been the subject of both experimental and theoretical studies due to its complex electronic structure resulting from vibronic interactions between its X̃2A2' and B̃2E' states. In particular, the definite assignment of the fundamental of its degenerate stretching vibration (ν3) is still under debate. Here, we report high-resolution photoelectron spectra of vibrationally pre-excited NO3- using the recently developed IR-cryo-SEVI technique. The anions are excited through infrared (IR) excitation near 1350 cm-1, accessing the ν3 and 2ν3(e') vibrational levels with band centers at 1350.5 and ∼2700 cm-1, respectively. The IR-cryo-SEVI spectrum for 2ν3 pre-excitation shows clear evidence for an intense 321 transition. From the position of this feature (30031 cm-1), the electron affinity of NO3 also determined in this work (31680 cm-1), and the IR excitation energy, we obtain a fundamental frequency of 1051 cm-1 for the ν3 fundamental of the NO3 radical. This assignment and other features in the IR-cryo-SEVI spectra are supported by spectral simulations based on a vibronic Köppel-Domcke-Cederbaum Hamiltonian. The simulations also show that nearly all features in the IR-cryo-SEVI spectra arise because of pseudo-Jahn-Teller coupling between the X̃ and B̃ states of NO3. The results and analysis presented here settle a long-standing controversy regarding the ν3 frequency of NO3.

Anions↗

New Subgrouping of Multiple Stellar Populations in NGC 2808 Based on Low-resolution Spectroscopy

We performed low-resolution spectroscopy for the red giant branch stars in an intriguing globular cluster (GC) NGC 2808, which hosts subpopulations with extreme helium and light-element abundances. In order to trace N, C, and Ca abundance differences among subpopulations, we measured CN, CH, and Ca ii H&K spectral indices, respectively. We identified four subpopulations (G1, G2, G3, and G4) from CN and CH strength, with CN-weak/CH-strong G1, CN-intermediate/CH-strong G2, CN-strong/CH-intermediate G3, and CN-strong/CH-weak G4. Compared to [Na/O] from high-resolution spectroscopy, we show that CN index can more clearly separate G1 and G2. Since CN traces N abundance in a GC, it implies that G1 and G2 would show a larger difference in [N/Fe] compared to [Na/Fe], as predicted by chemical evolution models. Later generation stars G3 and G4, however, are better separated with high-resolution spectroscopy. We also found that G4 shows a stronger Ca ii H&K line strength compared to that of G1, but we suspect this to be a result of unusually strong He enhancement and/or Mg depletion in G4 of this GC. This work illustrates that combining low- and high-resolution spectroscopic studies can improve the separation of subpopulations in GCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

A balloon-borne instrument for high-resolution astrophysical spectroscopy in the 20-8000 keV energy range

The Low Energy Gamma ray Spectrometer (LEGS) is designed to perform fine energy resolution measurements of astrophysical sources. The instrument is configured for a particular balloon flight with either of two sets of high purity germanium detectors. In one configuration, the instrument uses an array of three coaxial detectors (effective volume equal to or approximately 230 cubic cm) inside an NaI (T1) shield and collimator (field of view equal to or approximately 16 deg FWHM) and operates in the 80 to 8000 keV energy range. In the other configuration, three planar detectors (effective area equal to or approximately square cm) surrounded by a combination of passive Fe and active NaI for shielding and collimation (field of view equal to or approximately 5 deg x 10 deg FWHM) are optimized for the 20 to 200 keV energy range. In a typical one day balloon flight, LEGS sensitivity limit (3 sigma) for narrow line features is less than or approximately .0008 ph/cm/s square (coaxial array: 80 to 2000 keV) and less than or approximately .0003 ph/square cm/s (planar array: 50 to 150 keV).

Paciesas, W. S.↗

High resolution infrared spectroscopy: Some new approaches and applications to planetary atmospheres

The principles of spectral line formation and of techniques for retrieval of atmospheric temperature and constituent profiles are discussed. Applications to the atmospheres of Earth, Mars, Venus, and Jupiter are illustrated by results obtained with Fourier transform and infrared heterodyne spectrometers at resolving powers (lambda/delta hyperon lambda of approximately 10,000 and approximately 10 to the seventh power), respectively, showing the high complementarity of spectroscopy at these two widely different resolving powers. The principles of heterodyne spectroscopy are presented and its applications to atmospheric probing and to laboratory spectroscopy are discussed. Direct absorption spectroscopy with tuneable semiconductor lasers is discussed in terms of precision frequency-and line strength-measurements, showing substantial advances in laboratory infrared spectroscopy.

Mumma, M. J.↗

Circumnuclear ionized gas in starburst nuclei

In order to study kinematical properties of starburst nuclei (SBNs), researchers made high-resolution spectroscopy of fifteen SBNs in the H alpha region using an intensified Reticon system attached to the coude focus of the 188-cm reflector at the Okayama Astrophysical Observatory. The instrumental resolution is 21 km s(-1) Full Width Half Maximum (FWHM) at lambda sub H alpha. As for the archetypical SBN, Mrk 538 (=NGC 7714), researchers present high-resolution emission line profiles of several species of ions such as (OIII), (NII), (SII), and (OII). Main results and conclusions are summarized. It has been known that emission-line profiles of SBNs are symmetrical and narrow. However, this high-resolution spectroscopy shows that the observed emission-line profiles of the SBNs have the following asymmetrical patterns; blueward, redward, and double-peaked. It is known that such features have been observed for narrow line regions (NLRs) of active galactic nuclei (AGNs). There is no remarkable correlation between the asymmetry index and the reddening indicator such as a Balmer decrement. Thus the line asymmetry is not attributed to inhomogeneous obscuration in the emitting regions. The observed FWHMs of the H alpha emission lines cover a range from 85 km s(-1) to 318 km s(-1) and are slightly larger than those of (NII) lambda 6584A emission except for the double-peaked SBNs. The FWHMs of H alpha emission show a good correlation with sin i (i is an inclination angle of galaxy). This correlation means that the FWHMs of the SBNs suffer significantly from rotational broadening. Mrk 52 is an anomalous SBN because it has narrow emission line widths for its high inclination angle (cf. Taniguchi 1987). From the above correlation, it is estimated that the intrinsic (i.e., rotation free) FWHMs of H alpha emission are about 50 km s(-1).

Taniguchi, Yoshiaki↗

Numerical study of low-current steady arcs

The development of a high-efficiency CW YLF laser doped with Er,Tm,Ho: and featuring a strongly focusing resonator that collects a high density of pump power on the active crystal is described. The emission is investigated at 2.06 microns and a tuning range both at liquid-nitrogen (77 K) and at dry-ice (210 K) temperature. The noise characteristics and the long-term power stability of the laser is studied with an eye to employing this source for high-resolution spectroscopy in the 2-micron wavelength region. The detection of several absorption lines of NH3 at low pressure is described. The output power of the laser as a function of the power impinging on the crystal for different transmission of the output mirror is illustrated. The best result obtained is 1.46 W output for 3.2 W of argon pump. The minimum threshold achieved is 3.5 mW with a 1-percent transmission mirror. It is concluded that it is possible to develop a highly efficient Ho:YLF laser featuring low noise and sufficient tunability for high-resolution spectroscopy in the 2-micron region.

Kim, S. C.↗