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Free radical and overtone spectroscopy

In the fall of 1987 during a photoacoustic study of hydrogen peroxide's fourth vibrational overtone band, the remarkably clear and well resolved spectrum was observed. Its periodicity and K subband structure suggested that the spectrum was not of hydrogen peroxide but of a smaller near-prolate symmetric top molecule. Furthermore, the time dependent behavior of the signal indicated that chemical changes were taking place within the photoacoustic apparatus.

Reilly, James P.↗

Anharmonic Vibrational Spectroscopy of the F-(H20)n, complexes, n=1,2

We report anharmonic vibrational spectra (fundamentals, first overtones) for the F-(H(sub 2)O) and F-(H(sub 2)O)2 clusters computed at the MP2 and CCSD(T) levels of theory with basis sets of triple zeta quality. Anharmonic corrections were estimated via the correlation-corrected vibrational self-consistent field (CC-VSCF) method. The CC-VSCF anharmonic spectra obtained on the potential energy surfaces evaluated at the CCSD(T) level of theory are the first ones reported at a correlated level beyond MP2. We have found that the average basis set effect (TZP vs. aug-cc-pVTZ) is on the order of 30-40 cm(exp -1), whereas the effects of different levels of electron correlation [MP2 vs. CCSD(T)] are smaller, 20-30 cm(exp -1). However, the basis set effect is much larger in the case of the H-bonded O-H stretch of the F-(H(sub 2)O) cluster amounting to 100 cm(exp -1) for the fundamentals and 200 cm (exp -1) for the first overtones. Our calculations are in agreement with the limited available set of experimental data for the F-(H(sub 2)O) and F-(H(sub 2)O)2 systems and provide additional information that can guide further experimental studies.

Chaban, Galina M.↗

Intracavity Dye-Laser Absorption Spectroscopy (IDLAS) for application to planetary molecules

Time-resolved, quasi-continuous wave, intracavity dye-laser absorption spectroscopy is applied to the investigation of absolute absorption coefficients for vibrational-rotational overtone bands of water at visible wavelengths. Emphasis is placed on critical factors affecting detection sensitivity and data analysis. Typical generation-time dependent absorption spectra are given.

Lang, Todd M.↗

Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

Steinfeld, J. I.↗

Near-IR diode laser absorption for measurement of tropospheric HO2

The possibility of using tunable lead salt diode lasers in the infrared for measurement of tropospheric HO2 has been frequently considered. Although the sensitivity of diode laser absorption has been improved through the use of high frequency detection techniques, nature has been unkind in that the HO2 absorption cross sections are weak. Even using the most optimistic assumptions about attainable path length and detectable absorbance, measurement of tropospheric HO2 by diode laser absorption in the mid-IR appears marginal. A possible alternative method for measuring HO2 is by absorption at near-infrared wavelengths. Several absorption bands of HO2 occur in the wavelength region between 1.2 and 1.6 micron due to electronic transitions and overtones of the fundamental vibrational modes. InGaAsP diode lasers operate in this wavelength region and can be used for high resolution spectroscopy in a manner analogous to the lead salt lasers. A diode laser system in the near-IR offers some advantages.

Stanton, Alan C.↗

Detection Opportunity for Aromatic Signature in Titan's Aerosols in the 4.1-5.3 μm Range

The Cassini/Huygens mission provided new insights on the chemistry of the upper atmosphere of Titan. The presence of large molecules and ions (>100's of amu) detected by Cassini at high altitude was not expected, and questions the original assumptions regarding the aerosol formation pathways. From recent laboratory studies, it has been shown that the inclusion of trace amounts of aromatic species drastically impacts the chemistry of aerosol formation and induces observable changes in the properties of the aerosols. In this Letter we focus on the effect of one of the simplest nitrogenous aromatics, pyridine (C5H5N), on the infrared signature of Titan's aerosol analogs. We introduce initial gas mixtures of (i) N2–C5H5N (100%/250 ppm), (ii) N2–CH4–C5H5N (99%/1%/250 ppm), and (iii) N2–CH4 (99%/1%) in a cold plasma discharge. The material produced, herein called tholins, is then analyzed by mid-infrared spectroscopy. When adding pyridine in the discharge, the tholins produced present an aromatic signature in the 4.1–5.3 μm (1850–2450 cm−1) spectral region, attributed to overtones of aromatic C–H out-of-plane bending vibrations. We also observe a spectral shift of the nitrile and iso-nitrile absorption band with the inclusion of pyridine in the gas mixture. These results could help to investigate the data obtained at Titan by the Cassini/Visual and Infrared Mapping Spectrometer (VIMS) instrument in the 1–5 μm infrared window.

Mathé, Christophe↗

Development of an Early Warning Fire Detection System using Correlation Spectroscopy

Combustion byproducts are numerous. A few examples of the gaseous byproducts include carbon dioxide, carbon monoxide, hydrogen chloride, hydrogen cyanide and ammonia. For detecting these chemical species, classic absorption spectroscopy has been used for many decades, but the sensitivity of steady-state methods is often unsuitable for the detection of trace compounds at the low levels (parts per million to parts per billion) appropriate for scientific purposes. This is particularly so for monitoring equipment, which must be compact and cost-effective, and which is often subjected to shock, vibration, and other environmental effects that can severely degrade the performance of high-sensitivity spectrometers in an aircraft. Steady-state techniques also suffer from a lack of specificity; the deconvolution of the spectra of complex mixtures is a laborious and error prone process. These problems are exacerbated in remote fiber-optic monitoring where, for practical reasons, the fundamental absorbance region of the spectrum (often between 3 and 8 microns) is inaccessible, and the low-strength, closely spaced, near-infrared overtone absorbance bands must be used. We circumvented these challenges by employing correlation spectroscopy, a variation of modulation spectroscopy.

Goswami, K.↗

Allophane on Mars: Evidence from IR Spectroscopy and TES Spectral Models

Allophane is an alteration product of volcanic glass and a clay mineral precursor that is commonly found in basaltic soils on Earth. It is a poorly-crystalline or amorphous, hydrous aluminosilicate with Si/Al ratios ranging from approx.0.5-1 [Wada, 1989]. Analyses of thermal infrared (TIR) spectra of the Martian surface from TES show high-silica phases at mid-to-high latitudes that have been proposed to be primary volcanic glass [Bandfield et al., 2000; Bandfield, 2002; Rogers and Christensen, 2007] or poorly-crystalline secondary silicates such as allophane or aluminous amorphous silica [Kraft et al., 2003; Michalski et al., 2006; Rogers and Christensen, 2007; Kraft, 2009]. Phase modeling of chemical data from the APXS on the Mars Exploration Rover Spirit suggest the presence of allophane in chemically weathered rocks [Ming et al., 2006]. The presence of allophane on Mars has not been previously tested with IR spectroscopy because allophane spectra have not been available. We synthesized allophanes and allophanic gels with a range of Si/Al ratios to measure TIR emission and VNIR reflectance spectra and to test for the presence of allophane in Martian soils. VNIR reflectance spectra of the synthetic allophane samples have broad absorptions near 1.4 m from OH stretching overtones and 1.9 m from a combination of stretching and bending vibrations in H2O. Samples have a broad absorption centered near 2.25 microns, from AlAlOH combination bending and stretching vibrations, that shifts position with Si/Al ratio. Amorphous silica (opaline silica or primary volcanic glass) has been identified in CRISM spectra of southern highland terrains based on the presence of 1.4, 1.9, and broad 2.25 m absorptions [Mustard et al., 2008]; however, these absorptions are also consistent with the presence of allophane. TIR emission spectra of the synthetic allophanes show two spectrally distinct types: Si-rich and Al-rich. Si-rich allophanes have two broad absorptions centered near 1080 and 430 cm-1 from Si(Al)-O stretching and Si(Al)-O bending vibrations, respectively, and Al-rich allophanes have three broad absorptions centered near 950, 540, and 430 cm-1. We used a spectral library commonly used to deconvolve TES spectra and four allophane spectra to model nine spectrally distinct regions on Mars [from Rogers et al., 2007]. Regions previously modeled with high-silica phases contain significant amounts of allophane (>10 vol.%) in our models. Our models of northern Acidalia, the type locality for surface type 2 materials, contain 40 vol.% Si-rich allophane. The presence of allophane in multiple surface regions of Mars indicates a more widespread occurrence of low-temperature aqueous alteration at moderate pH than has been previously recognized. The regional variations in modeled abundances and the types of allophane (Si- vs. Al-rich) suggest regional differences in Mars weathering processes.

Ming, Douglas W.↗

Quantitative Species Measurements in Microgravity Combustion Flames using Near-Infrared Diode Lasers

Understanding the physical phenomena controlling the ignition and spread of flames in microgravity has importance for space safety as well as for characterizing dynamical and chemical combustion processes which are normally masked by buoyancy and other gravity-related effects. Unfortunately, combustion is highly complicated by fluid mechanical and chemical kinetic processes, requiring the use of numerical modeling to compare with carefully designed experiments. More sophisticated diagnostic methods are needed to provide the kind of quantitative data necessary to characterize the properties of microgravity combustion as well as provide accurate feedback to improve the predictive capabilities of the models. Diode lasers are a natural choice for use under the severe conditions of low gravity experiments. Reliable, simple solid state operation at low power satisfies the operational restrictions imposed by drop towers, aircraft and space-based studies. Modulation wavelength absorption spectroscopy (WMS) provides a means to make highly sensitive and quantitative measurements of local gas concentration and, in certain cases, temperature. With near-infrared diode lasers, detection of virtually all major combustion species with extremely rapid response time is possible in an inexpensive package. Advancements in near-infrared diode laser fabrication technology and concurrent development of optical fibers for these lasers led to their use in drop towers. Since near-infrared absorption line strengths for overtone and combination vibrational transitions are weaker than the mid-infrared fundamental bands, WMS techniques are applied to increase detection sensitivity and allow measurement of the major combustion gases. In the first microgravity species measurement, Silver et al. mounted a fiber-coupled laser at the top of the NASA 2.2-sec drop tower and piped the light through a single-mode fiber to the drop rig. A fiber splitter divided the light into eight channels that directed the laser beam across a methane or propane diffusion jet flame. The light beams were recaptured by a set of gradient index lenses, coupled back into separate fiber optic lines, and transmitted back to detectors and electronics in the instrument package. In these experiments a 6-mm od fiber cable (containing the nine optical fibers) fell with the drop rig. Using separate detection and demodulation channels, spatial and temporal (up to 20 Hz) maps of water vapor and methane concentrations were obtained at differing heights in the flames. While this apparatus was useful from a demonstration standpoint, several drawbacks needed attention before useful scientific measurements could be obtained. First, eight lines of sight are somewhat insufficient for detailing the spatial profiles of the gas. Second, multiple detection channels operating in parallel are both expensive and present a challenge for accurate calibration. As a result, a newer scanning system was developed in our first contract under this program. The primary characteristic of this system is that it contains a single detection channel and achieves "continuous" spatial resolution by scanning the laser beam across the flame region, then directing this beam onto a single detector. Thus spatial measurements are converted to a temporal series of data. The true spatial resolution is limited only by the beam diameter and width of the sweep. In these experiments the beam is focused to about 1-mm diameter and scans across a region up to 4-cm wide.

Silver, Joel A.↗

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↗

Vibrational Spectroscopy of Ions and Radicals Present in the Interstellar Medium and in Planetary Atmospheres: A Theoretical Study

Anharmonic vibrational frequencies and intensities are calculated for OH(H2O)n and H(H2O)n radicals (that form on icy particles of the interstellar medium), HCO radical (the main intermediate in the synthesis of organic molecules in space), NH2(-) and C2H(-) anions, H5(+) cation, and other systems relevant to interstellar chemistry. In addition to pure ions and radicals, their complexes with water are studied to assess the effects of water environment on infrared spectra. The calculations are performed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method with ab initio potential surfaces at the MP2 and CCSD(T) levels. Fundamental, overtone, and combination excitations are computed. The results are in good agreement with available experimental data and provide reliable predictions for vibrational excitations not yet measured in laboratory experiments. The data should be useful for interpretation of astronomically observed spectra and identification of ions and radicals present in the interstellar medium and in planetary atmospheres.

Chaban, Galina M.↗

Near-infrared spectroscopy of primitive solar system objects

We have obtained near-infrared (H and K band at lambda/Delta(lambda) is approximately 480 to 600) spectra of a sample of primitive objects including 2 Centaur objects (2060 Chiron and 5145 Pholus) and 16 P- and D-type asteroids. The spectra were obtained at the United Kingdom Infrared Telescope using the cooled grating spectrometer CGS4, and were used to search for chemically diagnostic vibrational features in these primitive objects. Pholus exhibits broad adsorption features at 2.07 and 2.27 micrometers, as well as a weak feature at 1.72 micrometers. The 1.72- and 2.27-micrometer features are similar to those seen in a laboratory tar sand sample. No distinct absorption features are found in other objects, including Chiron, which displays a spectrally neutral continuum. A comparison of the P- and D-type asteroid spectra with laboratory measurements of organic solids shows no compelling evidence for hydrocarbon overtones seen in terrestrial bituminous tar sands.

Luu, Jane↗

Laboratory Studies of the Photochemistry of Peroxynitric Acid

Observations of odd hydrogen radicals at high SZA in the lower stratosphere have demonstrated that our understanding of the HO(x) chemistry is incomplete [Wennberg et al., 1994a; Salawitch et al., 1994; Wennberg et al., 1999]. In particular, the concentrations of the HO(x) radicals are significantly larger than expected under weak photolytic conditions. Donaldson et al. [1997] have speculated that excitation of overtones of the OH stretching frequency in molecules such as HNO3 and HO2NO2 may be significant sources of HO(x) under these conditions. Although weak, vibrationally mediated photolysis may be important because it occurs in the near IR and visible and can provide energy in excess of the dissociation energy (D(o)): HONO2 + hv yields OH + NO (D(o) approx. 600 nm) and HOONO2 + hv yields OH + NO3 (D(o) approx. 735 nm) HOONO2 + hv yields HO2 + NO2 (D(o) approx. 1250 nm). In this project we developed instrumentation to characterize the photodissociation yields of hydroxyl containing compounds in the visible and near IR. This effort has involved coupling a tunable photolysis optical parametric oscillator (OPO) laser system with precise determination of the hydroxyl radical. The OPO system [Wu et al., 1997] was developed with support from the NSF Major Research Instrumentation Fund in a proposal entitled "Development of Novel, Compact Light Sources for Advanced Spectroscopy in Atmospheric Science and Materials Research" (Geoffrey A. Blake, P.I. California Institute of Technology).

Wennberg, Paul O.↗

Excited Vibrational Level Rotational Constants for SiC2: A Sensitive Molecular Diagnostic for Astrophysical Conditions

Silacyclopropynylidene, SiC2, is a known and highly abundant circumstellar molecule. Its spectrum has been established as a major component of lines observed toward the carbon-rich star IRC +10216 (CW Leonis). It has been detected in its low-lying v(sub 3) = 1 and 2 vibrational states as well as in various isotopic compositions. Increasing sensitivity and spatial resolution will enable many more emission or absorption lines to be detected. In order to detect new molecular species, unassigned lines of known species must be identified. This work uses established ab initio quartic force fields to produce data necessary for this classification of lines related to SiC2. Agreement between the theoretical vibrational frequencies and known rotational and spectroscopic constants is quite good, as good as 5 cm(exp -1) and 3 MHz, respectively in some cases. Additionally, experimentally unknown vibrational frequencies and rotational constants are provided for the first overtones and combination bands in addition to 3(sub v3), the second overtone of the low-lying antisymmetric stretch/carbide rotation mode. Frequencies of v(sub 3) = 3 low-J rotational transitions of the main isotopic species are also estimated from published data for v(sub 3) ≤ 2. Further, we determine rotational and centrifugal distortion parameters for which in most cases vibrational effects due to the v(sub 3) mode were reduced to first, and in several cases also to second order. These values may approximate equilibrium values better than the ground state values. The data produced herein will aid in the experimental and observational characterization of this known astromolecule in order to identify some of the unassigned lines for a known entity.

Astrochemistry↗