mid-IR Spectra Research Articles

DETECTIONS OF CO MOLECULAR GAS IN 24 μm BRIGHT ULIRGs ATz∼ 2 IN THESPITZERFIRST LOOK SURVEY

We present CO observations of 9 ULIRGs at z~2 with S(24\mu m)>1mJy, previously confirmed with the mid-IR spectra in the Spitzer First Look Survey. All targets are required to have accurate redshifts from Keck/GEMINI near-IR spectra. Using the Plateau de Bure millimeter-wave Interferometer (PdBI) at IRAM, we detect CO J(3-2) [7 objects] or J(2-1) [1 object] line emission from 8 sources with integrated intensities Ic ~(5-9)sigma. The CO detected sources have a variety of mid-IR spectra, including strong PAH, deep silicate absorption and power-law continuum, implying that these molecular gas rich objects at z~2 could be either starbursts or dust obscured AGNs. The measured line luminosity L'[CO] is (1.28-3.77)e+10[K km/s pc^2]. The averaged molecular gas mass M(H2) is 1.7e+10Msun, assuming CO-to-H2 conversion factor of 0.8Msun/[K km/s pc^2]. Three sources (33%) -- MIPS506, MIPS16144 & MIPS8342 -- have double peak velocity profiles. The CO double peaks in MIPS506 and MIPS16144 show spatial separations of 45kpc and 10.9kpc, allowing the estimates of the dynamical masses of 3.2e+11*sin^(-2)(i)Msun and 5.4e+11*sin^{-2}(i)Msun respectively. The implied gas fraction, M(gas)/M(dyn), is 3% and 4%, assuming an average inclination angle. Finally, the analysis of the HST/NIC2 images, mid-IR spectra and IR SED revealed that most of our sources are mergers, containing dust obscured AGNs dominating the luminosities at (3-6)um. Together, these results provide some evidence suggesting SMGs, bright 24um z~2 ULIRGs and QSOs could represent three different stages of a single evolutionary sequence, however, a complete physical model would require much more data, especially high spatial resolution spectroscopy.

SPITZERMID-INFRARED SPECTROSCOPY OF COMPACT SYMMETRIC OBJECTS: WHAT POWERS RADIO-LOUD ACTIVE GALACTIC NUCLEI?

We present low- and high-resolution mid-infrared (mid-IR) spectra and photometry for eight compact symmetric objects (CSOs) taken with the Infrared Spectrograph on the Spitzer Space Telescope. The hosts of these young, powerful radio galaxies show significant diversity in their mid-IR spectra. This includes multiple atomic fine-structure lines, H2 gas, polycyclic aromatic hydrocarbon (PAH) emission, warm dust from T = 50 to 150 K, and silicate features in both emission and absorption. There is no evidence in the mid-IR of a single template for CSO hosts, but 5/8 galaxies show similar moderate levels of star formation (<10 M_sun/yr from PAH emission) and silicate dust in a clumpy torus. The total amount of extinction ranges from A_V ~ 10 to 30, and the high-ionization [Ne V] 14.3 and 24.3 um transitions are not detected for any galaxy in the sample. Almost all CSOs show contributions both from star formation and active galactic nuclei (AGNs), suggesting that they occupy a continuum between pure starbursts and AGNs. This is consistent with the hypothesis that radio galaxies are created following a galactic merger; the timing of the radio activity onset means that contributions to the IR luminosity from both merger-induced star formation and the central AGN are likely. Bondi accretion is capable of powering the radio jets for almost all CSOs in the sample; the lack of [Ne V] emission suggests an advection-dominated accretion flow mode as a possible candidate. Merging black holes (BHs) with M_BH > 10^8 M_sun likely exist in all of the CSOs in the sample; however, there is no direct evidence from these data that BH spin energy is being tapped as an alternative mode for powering the radio jets.

Structural Basis of the 1H-Nuclear Magnetic Resonance Spectra of Ethanol–Water Solutions Based on Multivariate Curve Resolution Analysis of Mid-Infrared Spectra

The (1)H-nuclear magnetic resonance (NMR) chemical shifts of ethanol and water hydroxyl groups show a pattern change at a critical ethanol concentration. Below the critical value (20 mol% at 400 Hz), only one hydroxyl peak appears due to fast proton exchange, whereas above the critical concentration, the ethanol hydroxyl peak splits from the water peak emerging as an individual chemical shift. The structural basis of the NMR pattern change was interpreted by a multivariate curve resolution-alternating least squares (MCR-ALS) analysis of the mid-infrared (mid-IR) spectra obtained for ethanol-water solutions. Results suggest that the NMR pattern change is due to the formation of ethanol-ethanol clusters. Below the critical concentration, no ethanol-ethanol clusters exist. Therefore, the NMR does not detect the ethanol environment. Above the critical ethanol concentration, ethanol-ethanol clusters first appear such that a distinct ethanol hydroxyl peak emerges. The basis for the dependence of the critical concentration on working frequency is also interpreted. High frequency NMR measurements are more sensitive to ethanol content, resulting in a lower critical ethanol concentration.

Mid-infrared spectral variability for compositionally similar asteroids: Implications for asteroid particle size distributions

We report an unexpected variability among mid-infrared spectra (IRTF and Spitzer data) of eight S-type asteroids for which all other remote sensing interpretations (e.g. VNIR spectroscopy, albedo) yield similar compositions. Compositional fitting making use of their mid-IR spectra only yields surprising alternative conclusions: (1) these objects are not “compositionally similar” as the inferred abundances of their main surface minerals (olivine and pyroxene) differ from one another by 35% and (2) carbonaceous chondrite and ordinary chondrite meteorites provide an equally good match to each asteroid spectrum. Following the laboratory work of Ramsey and Christensen (Ramsey, M.S., Christensen, P.R. [1998]. J. Geophys. Res. 103, 577–596), we interpret this variability to be physically caused by differences in surface particle size and/or the effect of space weathering processes. Our results suggest that the observed asteroids must be covered with very fine (<5 μm) dust that masks some major and most minor spectral features. We speculate that the compositional analysis may be improved with a spectral library containing a wide variety of well characterized spectra (e.g., olivine, orthopyroxene, feldspar, iron, etc.) obtained from very fine powders. In addition to the grain size effect, space weathering processes may contribute as well to the reduction of the spectral contrast. This can be directly tested via new laboratory irradiation experiments.

Amide-I and -II Vibrations of the Cyclic β-Sheet Model Peptide Gramicidin S in the Gas Phase

In the condensed phase, the peptide gramicidin S is often considered as a model system for a beta-sheet structure. Here, we investigate gramicidin S free of any influences of the environment by measuring the mid-IR spectra of doubly protonated (deuterated) gramicidin S in the gas phase. In the amide I (i.e., C=O stretch) region, the spectra show a broad split peak between 1580 and 1720 cm(-1). To deduce structural information, the conformational space has been searched using molecular dynamics methods and several structural candidates have been further investigated at the density functional level. The calculations show the importance of the interactions of the charged side-chains with the backbone, which is responsible for the lower frequency part of the amide I peak. When this interaction is inhibited via complexation with two 18-crown-6 molecules, the amide I peak narrows and shows two maxima at 1653 and 1680 cm(-1). A comparison to calculations shows that for this complexed ion, four C=O groups are in an antiparallel beta-sheet arrangement. Surprisingly, an analysis of the calculated spectra shows that these beta-sheet C=O groups give rise to the vibrations near 1680 cm(-1). This is in sharp contrast to expectations based on values for the condensed phase, where resonances of beta-sheet sections are thought to occur near 1630 cm(-1). The difference between those values might be caused by interactions with the environment, as the condensed phase value is mostly deduced for beta-sheet sections that are embedded in larger proteins, that interact strongly with solvent or that are part of partially aggregated species.

Probing the specific interactions and structures of gas-phase vancomycin antibiotics with cell-wall precursor through IRMPD spectroscopy

Biomolecular recognition of vancomycin antibiotics with its cell-wall precursor analogue Ac(2)(L)K(D)A(D)A has been investigated in the gas phase through a combined laser spectroscopy/mass spectrometry approach. The mid-IR spectra (1100-1800 cm(-1)) of these mass-selected anionic species have been recorded by means of resonant infrared multiphoton dissociation (IRMPD) spectroscopy performed with the free-electron laser CLIO. Structural assignment has been achieved through comparisons with the low-energy conformers obtained from replica-exchange molecular dynamics simulations, for which IR spectra were calculated using a hybrid quantum mechanics/semi-empirical (QM/SE) method at the DFT/B3LYP/6-31+G*/AM1 level. Comparison between deprotonated vancomycin and its non-covalently bound V + Ac(2)(L)K(D)A(D)A complex shows significant spectral shifts of the carboxylate stretches and the Amide I and Amide II modes that are satisfactorily reproduced in the structures known from the condensed phase. Both theoretical and experimental findings provide strong evidence that the native structure of the deprotonated V + Ac(2)(L)K(D)A(D)A complex is preserved in the gas phase.

Formation of polycyclic aromatic hydrocarbon grains using anthracene and their stability under UV irradiation

It has been known for some time that the properties of a material are changed in nanometer size. Since it is nontrivial that polycyclic aromatic hydrocarbon (PAH) grains at the nanometer scale show similar properties with that of macroscopic scale, PAH grains were synthesized by a gas evaporation method and were analyzed using a transmission electron microscope and their UV-Vis and mid-IR spectra were measured. Results from these experiments showed that condensed anthracene grains from the gas phase had a planar form and showed similar infrared peaks compared to anthracene molecules, but with somewhat wider bands and different relative intensities. Some new features were also observed. The anthracene molecules formed photodimer in their grain and showed different infrared features after UV irradiation. This would be the first report concerning nanometersized PAH grains.

Syrian hamster embryo (SHE) assay (pH 6.7) coupled with infrared spectroscopy and chemometrics towards toxicological assessment

The Syrian hamster embryo (SHE) assay (pH 6.7) is an in vitro candidate to replace in vivo carcinogenicity tests. However, the conventional method of visual scoring of foci (non-transformed vs. transformed colonies) can be time-consuming and is open to subjectivity. Infrared (IR) spectroscopy has the potential to provide objective assessment of such SHE colonies with the added advantage of potentially providing mechanistic information. In this study, SHE cells were treated with one of eight different chemical regimens, allowed in culture to attach and form foci on IR-reflective glass slides; these were subsequently interrogated by attenuated total reflection (ATR) Fourier-transform IR (FTIR) spectroscopy. Derived mid-IR spectra (n = 13,406) were subjected to chemometric analysis focusing primarily on the extraction of biochemical information related to test agent treatment and/or morphological transformation. The use of ATR-FTIR spectroscopy with chemometrics to analyze the SHE assay is a novel approach to toxicological assessment.

The long-wavelength emission of interstellar PAHs: characterizing the spinning dust contribution

The emission of cold dust grains at long wavelengths will soon be observed by the Planck and Herschel satellites and provide new constraints on the nature of interstellar dust. The microwave anomalous emission, proposed to be due to spinning PAHs, should help to better define these species. Moreover, understanding the fluctuations of the anomalous emission over the sky is crucial for CMB studies. We focus on the long wavelength emission of interstellar PAHs in their rovibrational and rotational transitions. The PAH emission spectrum from the IR to the microwave range is presented and compared to anomalous emission observations. To model their long wavelength emission, we treat PAHs as isolated systems and follow consistently their IR and rotational emissions. We consider several interstellar phases and discuss how the anomalous emission may constrain their size distribution. Our model of PAH emission accounts for the mid-IR spectra of the diffuse interstellar medium and of the Orion Bar. For lambda<3mm the PAH IR emission does not scale any more with the radiation field intensity (Go) unlike the mid-IR part of the spectrum. This emission represents less than 10% of the total dust emission at 100 GHz. We find the broadband emissivity of spinning PAHs per carbon atom to be rather constant for Go<100 and nH<100cm-3. Observations of anomalous emission in the Perseus molecular cloud are explained by our model of spinning PAH emission with a standard abundance, supporting PAHs as the origin of the anomalous emission. The behaviour of the spinning dust emissivity with Go provides a clear test that can be tested against observations of anomalous and dust mid-IR emissions. Comparison of these emissions will provide constraints on the size and/or electric dipole moment of interstellar PAHs.

The formation and evolution of massive stellar clusters in IC4662

We present a multiwavelength study of the formation of massive stellar clusters, their emergence from cocoons of gas and dust, and their feedback on surrounding matter. Using data that span from radio to optical wavelengths, including Spitzer and Hubble Space Telescope ACS observations, we examine the population of young star clusters in the central starburst region of the irregular Wolf–Rayet galaxy IC4662. We model the radio-to-infrared (IR) spectral energy distributions of embedded clusters to determine the properties of their Hii regions and dust cocoons (sizes, masses, densities, temperatures), and use near-IR and optical data with mid-IR spectroscopy to constrain the properties of the embedded clusters themselves (mass, age, extinction, excitation, abundance). The two massive star-formation regions in IC4662 are excited by stellar populations with ages of ∼4 Myr and masses of ∼3×105 M⊙ (assuming a Kroupa initial mass function). They have high excitation and subsolar abundances, and they may actually be comprised of several massive clusters rather than the single monolithic massive compact objects known as ‘super star clusters’ (SSCs). Mid-IR spectra reveal that these clusters have very high extinction values, AV∼20–25 mag, and that the dust in IC4662 is well mixed with the emitting gas, not in a foreground screen.

THE MID-INFRARED CONTINUA OF SEYFERT GALAXIES

An analysis of archival mid-infrared (mid-IR) spectra of Seyfert galaxies from the Spitzer Space Telescope observations is presented. We characterize the nature of the mid-IR active nuclear continuum by subtracting a template starburst spectrum from the Seyfert spectra. The long wavelength part of the spectrum contains a strong contribution from the starburst-heated cool dust; this is used to effectively separate starburst-dominated Seyferts from those dominated by the active nuclear continuum. Within the latter category, the strength of the active nuclear continuum drops rapidly beyond ~ 20 micron. On average, type 2 Seyferts have weaker short-wavelength active nuclear continua as compared to type 1 Seyferts. Type 2 Seyferts can be divided into two types, those with strong poly-cyclic aromatic hydrocarbon (PAH) bands and those without. The latter type show polarized broad emission lines in their optical spectra. The PAH-dominated type 2 Seyferts and Seyfert 1.8/1.9s show very similar mid-IR spectra. However, after the subtraction of the starburst component, there is a striking similarity in the active nuclear continuum of all Seyfert optical types. PAH-dominated Seyfert 2s and Seyfert 1.8/1.9s tend to show weak active nuclear continua in general. A few type 2 Seyferts with weak/absent PAH bands show a bump in the spectrum between 15 and 20 micron. We suggest that this bump is the peak of a warm (~200 K) blackbody dust emission, which becomes clearly visible when the short-wavelength continuum is weaker. This warm blackbody emission is also observed in other Seyfert optical subtypes, suggesting a common origin in these active galactic nuclei.

CO2 Detection Using Microstructured Chalcogenide Fibers

In this work, detection in the mid-infrared (mid-IR) of carbon dioxide, so called greenhouse gas, using Fiber Evanescent Wave Spectroscopy (FEWS) technique is investigated. Since each pollutant gas shows a characteristic optical absorption spectrum in the mid-infrared, it is possible to detect selectively and quantitatively the presence of gases in a given environment by analysing mid-IR spectra. The main infrared signature of carbon dioxide gas consist in a double absorption peak located at 4.26 μm. Chalcogenide optical fibres, transmitting light in the 1-6 μm range, are well-adapted for CO2 analysis. Thus, tapered and microstructured chalcogenide fibers have especially been designed for CO2 detection. They present low optical losses in the spectral region of the CO2 absorption band. The fabrication of tapered and microstructured fibers is reported. Then, using a tapered fiber the detection limit of CO2 is around 20 vol.%. On the other hand, for the first time to our knowledge, the detection of gas in the mid-infrared is demonstrated with a chalcogenide microstructured fiber.

Low temperature CH4 and CO2 clathrate hydrate near to mid-IR spectra

AbstractThe physical behaviour of methane and carbon dioxide clathrate hydrates, specific crystallographic ice crystals are of major importance for the earth and may control the stability of gases in many astrophysical bodies such as the planets, comets and possibly interstellar grains. Such models claim they provide an alternative trapping mechanism modifying the absolute and relative composition of icy bodies and can be at the source of late time injection of gaseous species in planetary atmospheres. However, there is a clear need to detect them directly. We provide in this study the laboratory recorded signatures of clathrate hydrates in the near to mid-infrared for astrophysical remote detection. These laboratory experiments will in a near future allow to follow the kinetic formation by diffusion in dedicated experiments, another important step to implement, to understand and model their possible presence in space.

High-Pressure Far- and Mid-Infrared Study of 1,3,5-Triamino-2,4,6-trinitrobenzene

Synchrotron infrared measurements of 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) have been performed in the far-IR and mid-IR spectral regions up to approximately 30 and approximately 40 GPa, respectively. For the far-IR experiment, no pressurizing medium was used, whereas KBr was utilized as a pressurizing medium for the mid-IR experiment. For both experiments, pressure was cycled and IR spectra were recorded at various pressures to ascertain sample survival. In the high frequency region (approximately 3000 cm(-1)) of the mid-IR spectra, the peak frequencies of the NH2 symmetric and antisymmetric vibrational modes steadily decrease with increasing pressure, indicating strengthening of intermolecular hydrogen bonding with pressure. In both experiments, no apparent phase transition was observed to the highest pressures studied.

THE INFRARED SPECTRA OF VERY LARGE IRREGULAR POLYCYCLIC AROMATIC HYDROCARBONS (PAHs): OBSERVATIONAL PROBES OF ASTRONOMICAL PAH GEOMETRY, SIZE, AND CHARGE

The mid-IR spectra of six large, irregular PAHs with formulae (C84H24 - C120H36) have been computed using Density Functional Theory (DFT). Trends in the dominant band positions and intensities are compared to those of large, compact PAHs as a function of geometry, size and charge. Irregular edge moieties that are common in terrestrial PAHs, such as bay regions and rings with quartet hydrogens, are shown to be uncommon in astronomical PAHs. As for all PAHs comprised solely of C and H reported to date, mid-IR emission from irregular PAHs fails to produce a strong CCstr band at 6.2 um, the position characteristic of the important, class A astronomical PAH spectra. Earlier studies showed inclusion of nitrogen within a PAH shifts this to 6.2 um for PAH cations. Here we show this band shifts to 6.3 um in nitrogenated PAH anions, close to the position of the CC stretch in class B astronomical PAH spectra. Thus nitrogenated PAHs may be important in all sources and the peak position of the CC stretch near 6.2 um appears to directly reflect the PAH cation to anion ratio. Large irregular PAHs exhibit features at 7.8 um but lack them near 8.6 um. Hence, the 7.7 um astronomical feature is produced by a mixture of small and large PAHs while the 8.6 um band can only be produced by large compact PAHs. As with the CCstr, the position and profile of these bands reflect the PAH cation to anion ratio.

On-Line Fourier Transform Infrared Spectrometric Detection in Gradient Capillary Liquid Chromatography Using Nanoliter-Flow Cells

A capillary liquid chromatographic system has been successfully interfaced with a mid-IR Fourier transform infrared (FT-IR) spectrometer. Spectra were recorded on-line using a micromachined transmission CaF(2) cell (internal volume of 7.5 nL) that was placed on a dedicated beam condenser attached to the spectrometer. Linear gradients were run from (50:50) to (35:65) water (0.05% TFA)/acetonitrile in 15 min for the separation of standard solutions of four nitrophenols (4-nitrophenol, 3-methyl-4-nitrophenol, 2,4-dinitrophenol, and 2-nitrophenol) in a reversed phase system, providing limits of detection between 35 and 94 ng on-column. The changing background absorption due to gradient elution was successfully corrected by using a dedicated algorithm implemented in Matlab. When this chemometric data treatment was used, highly characteristic analyte spectra could be recorded as indicated by correlation coefficients between 89 and 95.8%, obtained when comparing mid-IR spectra of standard solutions and the spectra extracted from the chromatogram.

ERRATUM: “THE 5.25 AND 5.7 μm ASTRONOMICAL POLYCYCLIC AROMATIC HYDROCARBON EMISSION FEATURES” (2009, ApJ, 690, 1208)

Astronomical mid-IR spectra show two minor PAH features at 5.25 and 5.7 $\mu$m (1905 and 1754 cm$^{\rm - 1}$) that hitherto have been little studied, but contain information about the astronomical PAH population that complements that of the major emission bands. Here we report a study involving both laboratory and theoretical analysis of the fundamentals of PAH spectroscopy that produce features in this region and use these to analyze the astronomical spectra. The ISO SWS spectra of fifteen objects showing these PAH features were considered for this study, of which four have sufficient S/N between 5 and 6 $\mu$m to allow for an in-depth analysis. All four astronomical spectra show similar peak positions and profiles. The 5.25 $\mu$m feature is peaked and asymmetric, while the 5.7 $\mu$m feature is broader and flatter. Detailed analysis of the laboratory spectra and quantum chemical calculations show that the astronomical 5.25 and 5.7 $\mu$m bands are a blend of combination, difference and overtone bands primarily involving CH stretching and CH in-plane and CH out-of-plane bending fundamental vibrations. The experimental and computational spectra show that, of all the hydrogen adjacency classes possible on PAHs, solo and duo hydrogens consistently produce prominent bands at the observed positions whereas quartet hydrogens do not. In all, this a study supports the picture that astronomical PAHs are large with compact, regular structures. From the coupling with primarily strong CH out-of-plane bending modes one might surmise that the 5.25 and 5.7 $\mu$m bands track the neutral PAH population. However, theory suggests the role of charge in these astronomical bands might also be important.

Detection of adulteration of extra-virgin olive oil by chemometric analysis of mid-infrared spectral data

This study focuses on the detection and quantification of extra-virgin olive oil adulteration with different edible oils using mid-infrared (IR) spectroscopy with chemometrics. Mid-IR spectra were manipulated with wavelet compression previous to principal component analysis (PCA). Detection limit of adulteration was determined as 5% for corn-sunflower binary mixture, cottonseed and rapeseed oils. For quantification of adulteration, mid-IR spectral data were manipulated with orthogonal signal correction (OSC) and wavelet compression before partial least square (PLS) analysis. The results revealed that models predict the adulterants, corn-sunflower binary mixture, cottonseed and rapeseed oils, in olive oil with error limits of 1.04, 1.4 and 1.32, respectively. Furthermore, the data were analysed with a general PCA model and PLS discriminant analysis (PLS-DA) to observe the efficiency of the model to detect adulteration regardless of the type of adulterant oil. In this case, detection limit for adulteration is determined as 10%.

INFRARED SPECTRA OF AMMONIA-WATER ICES

We conducted a systematic study of the near-IR and mid-IR spectra of ammonia–water ices at various NH3/ H2O ratios. The differences between the spectra of amorphous and crystalline ammonia–water ices were also investigated. The 2.0 μm ammonia band central wavelength is a function of the ammonia/water ratio. It shifts from 2.006 ± 0.003 μm (4985 ± 5c m −1 ) to 1.993 ± 0.003 μm (5018 ± 5c m −1 ) as the percentage of ammonia decreases from 100% to 1%. The 2.2 μm ammonia band center shifts from 2.229 ± 0.003 μm (4486 ± 5c m −1 )t o 2.208 ± 0.003 μm (4528 ± 5c m −1 ) over the same range. Temperature-dependent shifts of those bands are below the uncertainty of the measurement, and therefore are not detectable. These results are important for comparison with astronomical observations as well as for estimating the concentration of ammonia in outer solar system ices.

Model infrared spectra of passively heated proto-planetary disks surrounding intermediate-mass pre-main-sequence stars

Aims. We study theoretical spectra at mid-infrared (5−40 μm) wavelengths of proto-planetary disks surrounding intermediate-mass pre-main-sequence stars. Observations show a wide range of spectral shapes and a rich variety in strength and shape of dust resonances. These strong variations in spectral shape reflect differences in the nature and spatial distribution of dust particles in the disk. The aim of this study is to establish what model parameters influence the mid-IR spectra of planet-forming disks. Methods. A grid of models of passively heated proto-planetary disks is used to calculate the infrared spectrum. We use hydrostatic equilibrium disk models and radiative transfer to calculate the emerging spectrum. We focus on the effects that different disk geometries (flaring, self-shadowed) and dust mineralogy have on the emerging 5−40 μm spectrum. We adopt four scenarios for the radial and vertical distribution of crystalline silicate dust. Results. In our model, the 23.5 μm forsterite band is more sensitive to emission from regions 5 percent) of crystalline silicates at a long distance from the star (>20−50 AU) show detectable emission in the 33.5 μm forsterite band. The carbon-dust abundance affects the strength of the dust resonances in the 10 μm spectral region, but not in the 30 μm region.