Mapping the Gold Butte Block with Visible Through Thermal Infrared Spectroscopy
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MODIS/ASTER MASTER AVIRIS Thermal Infrared Spectro↗
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Probing electrolyte–silica interactions through simulations of the infrared spectroscopy of nanoscale pores
The structural and dynamical properties of nanoconfined solutions can differ dramatically from those of the corresponding bulk systems. Understanding the changes induced by confinement is central to controlling the behavior of synthetic nanostructured materials and predicting the characteristics of biological and geochemical systems. A key outstanding issue is how the molecular-level behavior of nanoconfined electrolyte solutions is reflected in different experimental, particularly spectroscopic, measurements. This is addressed here through molecular dynamics simulations of the OH stretching infrared (IR) spectroscopy of NaCl, NaBr, and NaI solutions in isotopically dilute HOD/D 2 O confined in hydroxylated amorphous silica slit pores of width 1–6 nm and pH ~2. In addition, the water reorientation dynamics and spectral diffusion, accessible by pump–probe anisotropy and two-dimensional IR measurements, are investigated. In this work, the aim is to elucidate the effect of salt identity, confinement, and salt concentration on the vibrational spectra. It is found that the IR spectra of the electrolyte solutions are only modestly blue-shifted upon confinement in amorphous silica slit pores, with both the size of the shift and linewidth increasing with the halide size, but these effects are suppressed as the salt concentration is increased. This indicates the limitations of linear IR spectroscopy as a probe of confined water. However, the OH reorientational and spectral diffusion dynamics are significantly slowed by confinement even at the lowest concentrations. The retardation of the dynamics eases with increasing salt concentration and pore width, but it exhibits a more complex behavior as a function of halide.
Mesoporous material↗
Study of polyphenyl ether fluid /5P4E/ in operating elastohydrodynamic contacts by infrared emission spectroscopy
Infrared emission spectra of 5P4E polyphenyl ether were obtained from an operating elastohydrodynamic sliding contact at different speeds and loads by Fourier emission microspectrophotometry. The spectra were found to be polarized with respect to the direction of the conjunction line, especially at high shear rates. Film and metal surface temperatures were calculated from the spectra, and film thicknesses were determined under various operating conditions. Changes of polarized band structure above a critical shear rate, at which the slope of the film temperature versus shear curve changes abruptly and at which the film thickness assumes a minimum value, are consistent with a transition of the lubricant from a viscous liquid to a viscoelastic liquid or to an elastic solid.
Lauer, J. L.↗
Chemical modification of TiO2 surfaces with methylsilanes and characterization by infrared absorption spectroscopy
Infrared absorption spectra of methylsilanes bonded to a TiO2 powder were obtained. The reacting silanes include Me sub (4-n)SiX sub n (n=1-4; X=Cl, OMe) and hexamethyldisilazane (HMDS). Reactions were performed on hydroxylated-but-anhydrous TiO2 surfaces in the gas phase. IR spectra confirm the presence of a bonded silane layer. Terminal surface OH groups are found to react more readily than bridging OH groups. By-products of the modification adsorp tenaciously to the surface. The various silanes show only small differences in their ability to sequester surface OH groups. Following hydrolysis in moist air, Si-OH groups are observed only for the tetrafunctional silanes.
Finklea, H. O.↗
Extragalactic infrared spectroscopy
The spectra of galaxies in the near infrared atmospheric transmission windows are explored. Emission lines were detected due to molecular hydrogen, atomic hydrogen recombination lines, a line attributed to FEII, and a broad CO absorption feature. Lines due to H2 and FEII are especially strong in interacting and merging galaxies, but they were also detected in Seyferts and normal spirals. These lines appear to be shock excited. Multi-aperture measurements show that they emanate from regions as large as 15 kpc. It is argued that starbursts provide the most plausible and consistent model for the excitation of these lines, but the changes of relative line intensity of various species with aperture suggest that other excitation mechanisms are also operating in the outer regions of these galaxies.
Joseph, R. D.↗
Infrared spectroscopy (2.3-20 microns) for the geological interpretation of remotely-sensed multispectral thermal infrared data
The spectral radiance and spectral reflectance of natural weathered surfaces of common sedimentary and igneous rocks is determined from in situ and in the laboratory measurements. In situ spectral radiance measurements (5-14 microns) were made with a portable spectral radiometer and were used to derive the spectral emissivity of the rocks. The spectral reflectance measurements (2.3-20 microns) were made in a laboratory with a Fourier transform IR spectrometer with a diffuse reflectance accessory. Good agreement is found between the two techniques. The field portable spectrometer has a larger field of view and the in situ data provide more accurate measurements of the intensity of spectral features related to temperature and atmospheric effects.
Bartholomew, Mary Jane↗
Balloon-borne Infrared Telescope (BIRT) for far-infrared spectroscopy
The Japanese-made Balloon-borne Infrared Telescope (BIRT) designed for FIR astronomy is described. The BIRT system includes a 50-cm-diam telescope; an attitude-control system consisting of an attitude stabilization and a pointing and tracking subsystems; the ground support system consisting of four personal-computer systems; and electronics consisting of three small computer systems, servo circuits, power amplifiers, and other small circuits. Between 1985 and 1988, the BIRT has flown eight times, demonstrating that it is able to provide a suitable telescope observations on a stable platform with a long integration time. Structural diagrams of the BIRT overall system, the optical system, and the wobbling mechanism are presented along with a block diagram of the on-board electronics.
Shibai, Hiroshi↗
Excitation of the E2 and W1 "Arched" Filaments Near the Galactic Center as Deduced from Far-Infrared Spectroscopy
We present measurements of the far-infrared (FIR) fine structure lines [S III] (33 microns), [Si II] (35 microns), [O III] (51, 88 microns), [O I] (63 microns) and [C II] (158 microns) and the adjacent continua along a scan crossing the E2 and W1 thermal radio filaments in the Galactic center 'Arc'. The deduced electron density and excitation vary along the scan by less than factors of two and three, respectively. The properties of the two filaments are similar: the line and continuum fluxes peak at the radio ridge, and the ridge/off-ridge contrast is greatest for the FIR continuum and ionized lines, lower for the single dish radio measurements (Sofue et al. 1986), and smallest for the low excitation lines. The spatial coincidence of the FIR and radio peaks demonstrates that any excitation mechanism for the radio continuum filaments must also account for the FIR line and continuum emission. The FIR luminosity of approx. 3 x 10(exp 5) Solar Luminosity per beam, and the association of [O III] emission with the filaments poses difficulties for shock and MHD models. Photoionization of molecular cloud edges by a random distribution of stars is the most likely excitation mechanism among those proposed. The continuum and the low excitation line fluxes are consistent with an origin in photodissociated molecular material adjacent to the photoionized gas.
Colgan, Sean W.J.↗
Peripherally hydrogenated neutral polycyclic aromatic hydrocarbons as carriers of the 3 micron interstellar infrared emission complex: results from single-photon infrared emission spectroscopy
Infrared emission spectra of five gas-phase UV laser-excited polycyclic aromatic hydrocarbons (PAHs) containing aliphatic hydrogens are compared with the main 3.3 microns and associated interstellar unidentified infrared emission bands (UIRs). We show that neutral PAHs can account for the majority of the 3 microns emission complex while making little contribution to the other UIR bands; peripherally hydrogenated PAHs produce a better match to astrophysical data than do those containing methyl side groups; 3.4 microns plateau emission is shown to be a general spectral feature of vibrationally excited PAHs containing aliphatic hydrogens, especially those containing methyl groups; and finally, hot-band and overtone emissions arising from aromatic C-H vibrations are not observed in laboratory emission spectra, and therefore, in contrast to current assignments, are not expected to be observed in the UIRs.
NASA Discipline Exobiology↗
Structures of aspartic acid-96 in the L and N intermediates of bacteriorhodopsin: analysis by Fourier transform infrared spectroscopy
The light-induced difference Fourier transform infrared spectrum between the L or N intermediate minus light-adapted bacteriorhodopsin (BR) was measured in order to examine the protonated states and the changes in the interactions of carboxylic acids of Asp-96 and Asp-115 in these intermediates. Vibrational bands due to the protonated and unprotonated carboxylic acid were identified by isotope shift and band depletion upon substitution of Asp-96 or -115 by asparagine. While the signal due to the deprotonation of Asp-96 was clearly observed in the N intermediate, this residue remained protonated in L. Asp-115 was partially deprotonated in L. The C = O stretching vibration of protonated Asp-96 of L showed almost no shift upon 2H2O substitution, in contrast to the corresponding band of Asp-96 or Asp-115 of BR, which shifted by 9-12 cm-1 under the same conditions. In the model system of acetic acid in organic solvents, such an absence of the shift of the C = O stretching vibration of the protonated carboxylic acid upon 2H2O substitution was seen only when the O-H of acetic acid is hydrogen-bonded. The non-hydrogen-bonded monomer showed the 2H2O-dependent shift. Thus, the O-H bond of Asp-96 enters into hydrogen bonding upon conversion of BR to L. Its increased hydrogen bonding in L is consistent with the observed downshift of the O-H stretching vibration of the carboxylic acid of Asp-96.
NASA Discipline Exobiology↗
Near-infrared spectroscopy of planetary nebulae: How strong is the H2 emission?
In an effort to understand the systematics of the H2 emission from planetary nebulae, a program of near-infared spectroscopy using the University of Texas infrared reticon spectrometer was started. This instrument has a 1x32 element InSb photodiode array as a detector. All of the observations reported were made on the McDonald Observatory 2.7 m telescope, with spectra resolving power lambda/delta lambda = 600. The spectral coverage allows the measurement strengths of Brackett gamma He I 2.113 microns, HE II 2.189 microns and the v = 1=0 S(1) line of H2 at 2.122 microns. One of the most important advantages of this instrument is that we are able to resolve H2 from the adjacent He I line. Most previous observations of planetaries have been made at spectral resolving powers of about 100, which blend these lines. The contribution of the He I line has generally been dismissed as being unimportant, but we show that this may not be valid. Our higher resolving power also improves the line-to-continuum contrast; in some cases, the continuum is the limiting factor in detecting faint lines.
Dinerstein, H. L.↗
High-Resolution Near-Infrared Spectroscopy of an Equivalent Width-Selected Sample of Starbursting Dwarf Galaxies
Spectroscopic observations from the Large Binocular Telescope and the Very Large Telescope reveal kinematically narrow lines (approx. 50 km/s) for a sample of 14 Extreme Emission Line Galaxies (EELGs) at redshifts 1.4 < zeta < 2.3. These measurements imply that the total dynamical masses of these systems are low ( 3 × 10(exp 9) M). Their large [O III]5007 equivalent widths (500 − 1100 A) and faint blue continuum emission imply young ages of 10−100 Myr and stellar masses of 10(exp 8)−10(exp 9) M, confirming the presence of a violent starburst. The stellar mass formed in this vigorous starburst phase thus represents a large fraction of the total (dynamical) mass, without a significantly massive underlying population of older stars. The occurrence of such intense events in shallow potentials strongly suggests that supernova-driven winds must be of critical importance in the subsequent evolution of these systems.
Spectroscopy↗
Photodissociation and Infrared Spectroscopy of Uranium–Nitrogen Cation Complexes
Laser vaporization of uranium in a pulsed supersonic expansion of nitrogen is used to produce complexes of the form U + (N 2 ) n (n = 1–8). These ions are mass selected in a reflectron time-of-flight spectrometer and studied with visible and UV laser fixed-frequency photodissociation and with tunable infrared laser photodissociation spectroscopy. The dissociation patterns and spectroscopy of U + (N 2 ) n indicate that N 2 ligands are intact molecules and that there is no insertion chemistry resulting in UN + or NUN + . Fixed frequency photodissociation at 532 and 355 nm indicate that the U + –N 2 bond dissociation energy varies little with changing coordination. The photon energy and the number of ligands eliminated allow an estimate of the average U + –N 2 dissociation energy of 12 kcal/mol. Infrared bands are observed for these complexes near the N–N stretch vibration via elimination of N 2 molecules. These resonances are observed to be shifted about 130 cm–1 to the red from the free-N 2 frequency for complexes with n = 3–8. Density functional theory indicates that U + is most stable in the sextet state in these complexes and that N 2 molecules bind in end-on configurations. Furthermore, the fully coordinated complex is predicted to be U + (N 2 ) 8 , which has a cubic structure. The vibrational frequencies predicted by theory are consistently lower than those in the experiment, independent of the isomeric structure or spin state of the complexes. Despite its failure to reproduce the infrared spectra, theory provides an average U + –N 2 dissociation energy of 11.8 ± 0.5 kcal/mol, in good agreement with the value from the experiments.
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
Using mid-infrared spectroscopy to estimate soil microbial properties at the continental scale
Understanding microbial community properties is critical to improving the predictions of biogeochemical processes for enhancing soil carbon sequestration. Here, in this observational study, mid-infrared (MIR) spectroscopy and partial least squares regression was used to predict soil microbial and chemical properties from diverse ecosystems across the continental USA. Random calibration and validation demonstrated the prediction potential for soil properties using MIR spectra, with the strongest predictions for microbial respiration, followed by microbial biomass carbon and nitrogen, ß-glucosidase activity, as well as soil chemical properties including organic carbon and total nitrogen. Microbial properties were mainly positively correlated to spectral regions associated with aliphatic C-H groups and C=O stretches of polysaccharides and negatively correlated to quartz and silicate-associated regions. We conclude that MIR spectroscopy can characterize soil microbial functions and be useful for the improvement of continental-scale soil carbon modeling and prediction programs.
59 BASIC BIOLOGICAL SCIENCES↗
Infrared spectroscopy of RG–Co + (H 2 O) complexes (RG = Ar, Ne, He): The role of rare gas “tag” atoms
RG n –Co + (H 2 O) cation complexes (RG = Ar, Ne, He) are generated in a supersonic expansion by pulsed laser vaporization. Here, complexes are mass-selected using a time-of-flight spectrometer and studied with infrared laser photodissociation spectroscopy, measuring the respective mass channels corresponding to the elimination of the rare gas “tag” atom. Spectral patterns and theory indicate that the structures of the ions with a single rare gas atom have this bound to the cobalt cation opposite the water moiety in a near-C 2v arrangement. The O–H stretch vibrations of the complex are shifted compared to those of water because of the metal cation charge-transfer interaction; these frequencies also vary systematically with the rare gas atom attached. The efficiencies of photodissociation also vary with the rare gas atoms because of their widely different binding energies to the cobalt cation. The spectrum of the argon complex could only be measured when at least three argon atoms were attached. In the case of the helium complex, the low binding energy allows the spectra to be measured for the low-frequency H–O–H scissors bending mode and for the O–D stretches of the deuterated analog. The partially resolved rotational structure for the antisymmetric O–H and O–D stretches reveals the temperature of these complexes (6 K) and establishes the electronic ground state. The helium complex has the same 3 B 1 ground state as the tag-free complex studied previously by Metz and co-workers (2013), but the A rotational constant is contaminated by vibrational averaging from the bending motion of the helium.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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.↗
High-resolution near-infrared spectroscopy of water dimer
High-resolution near-infrared spectra are reported for all of the O-H stretch vibrational bands of the water dimer. The four O-H vibrations are characterized as essentially independent proton-donor or proton-acceptor motions. In addition to the rotational and vibrational information contained in these spectra, details are obtained concerning the internal tunneling dynamics in both the ground and excited vibrational states. These results show that, for tunneling motions which involve the interchange of the proton donor and acceptor molecules, the associated frequencies decrease substantially due to vibrational excitation. The predissociation lifetimes for the various states of the dimer are determined from linewidth measurements. These results clearly show that the predissociation dynamics is strongly dependent on the tunneling states, as well as the Ka quantum number, indicating that the internal tunneling dynamics plays an important role in determining the dissociation rate in this complex.
Huang, Z. S.↗
2-45 Micron Infrared Spectroscopy of Carbon-Rich Proto-Planetary Nebulae
Infrared Space Observatory (ISO) 2-45 micron observations of seven proto-planetary nebulae (PPNs) and two other carbon-rich objects are presented. The unidentified emission features at 21 and 30 microns are detected in six sources, including four new detections of the 30 micron feature. This previously unresolved 30 micron feature is now resolved and found to consist of a broad feature peaking at 27.2 microns (the '30 micron' feature) and a narrower feature at 25.5 microns (the '26 micron' feature). This new 26 micron feature is detected in eight sources and is particularly strong in IRAS Z02229 + 6208 and 16594-4656. The unidentified infrared (UIR) emission features at 3.3, 6.2, 7.7, and 11.3 microns which are commonly observed in planetary nebulae and H II regions, are also seen in these PPNs. However, their strengths relative to the continuum plateaus at 8 and 12 microns are weaker than in planetary nebulae. The 6.9 micron feature, seen almost exclusively in PPNs, is strong. New millimeter CO and HCN observations were made; they support the carbon-rich nature of the objects and yield the expansion velocities of the gaseous envelopes. The spectral energy distributions of these PPNs were fitted with a radiative-transfer model, taking into account the emission features at 21, 26, and 30 microns. A significant fraction of the total energy output is emitted in these features: as high as 20% in the 30 micron feature and 8% in the 21 micron feature. The fact that so much energy is carried in these features suggests that the material responsible for these features must be made of abundant elements and most likely involves carbon. SiS, appears to be ruled out as the emitter of the 21 micron feature due to the absence of a predicted companion feature.
Hrivnak, Bruce J.↗