Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Vibrational Spectroscopy”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 235 records · Page 13
All sourcesNASA NTRSDOE OSTI
NASA NTRS2016

High-Resolution IR Absorption Spectroscopy of Polycyclic Aromatic Hydrocarbons: The Realm of Anharmonicity

We report on an experimental and theoretical investigation of the importance of anharmonicity in the 3 micrometers CH stretching region of Polycyclic Aromatic Hydrocarbon (PAH) molecules. We present mass-resolved, high-resolution spectra of the gas-phase cold ((is) approximately 4K) linear PAH molecules naphthalene, anthracene, and tetracene. The measured IR spectra show a surprisingly high number of strong vibrational bands. For naphthalene, the observed bands are well separated and limited by the rotational contour, revealing the band symmetries. Comparisons are made to the harmonic and anharmonic approaches of the widely used Gaussian software. We also present calculated spectra of these acenes using the computational program SPECTRO, providing anharmonic predictions enhanced with a Fermi-resonance treatment that utilizes intensity redistribution. We demonstrate that the anharmonicity of the investigated acenes is strong, dominated by Fermi resonances between the fundamental and double combination modes, with triple combination bands as possible candidates to resolve remaining discrepancies. The anharmonic spectra as calculated with SPECTRO lead to predictions of the main modes that fall within 0.5% of the experimental frequencies. The implications for the Aromatic Infrared Bands, specifically the 3-m band are discussed.

Astrochemistry↗
NASA NTRS1984

Interstellar Grain Mantles

Techniques for determining the composition of small dust grains in interstellar matter are discussed. The best way to study the composition of interstellar grain mantles is by infrared spectroscopy. The absorption features in a complete infrared spectrum from 2 to 15 microns can be used as fingerprints to identify the absorbing molecule. Ground-based observations around 3 microns confirmed the presence of H2O ice in interstellar grain mantles, through the detection of the 3.08 micron OH stretching vibration. The detection of other molecules, in particular the carbon bearing molecules, is however hampered by atmospheric absorption in the 5-8 micron region and the presence of the strong ice and silicate bands, which dominate the 3 and 10 micron region respectively. Kuiper Airborne Observatory observations of the 5-8 micron region of the spectrum are therefore extremely important to determine the composition of interstellar grain mantles. The 5 to 8 micron spectra of molecular cloud sources was obtained using a 24 detector grating spectrometer. An important characteristic of this spectrometer is that the whole spectrum is obtained simultaneously. It is therefore relatively easy to correct for atmospheric transmission.

Witteborn, F.↗
NASA NTRS1989

Jet-resolved vibronic structure in the higher excited states of N2O - Ultraviolet three-photon absorption spectroscopy from 80,000 to 90,000/cm

Ionization-detected UV multiphoton absorption spectroscopy of the excited states of N2O is presented, showing Rydberg structure within 20,000/cm of the first ionization threshold. Despite evidence for strong Rydberg-continuum coupling in the form of broadened bands and Fano line-shapes, the Rydberg structure persists, with atomic-like quantum defects and vibration structure well-matched with that of the ion. In the most clearly resolved spectrum, corresponding to the 3p(delta)1Pi state, Renner-Teller and Herzberg-Teller coupling of electronic and vibrational angular momentum are revealed. It is suggested that these mixings are properties of the N2O(+)Pi ion core.

Patsilinakou, E.↗
NASA NTRS1989

Stable isotope laser spectroscopy

Recent advances in semiconductor laser technology have produced a reliable lightweight device ideally suited for a spacecraft high resolution molecular spectrometer. Lead-salt tunable diode lasers (TDL) emit in several spectral modes, each with a very narrow linewidth of -0.0003/cm. This spectral resolution is much narrower than typical Doppler broadened molecular linewidths in the mid-IR range. Thus it is possible to detect individual rotational lines within the vibrational band and measure their intensity, which can be used to determine gas concentration. The narrow spectral lines of any impurity gas tend to lie between the narrow lines of the gas of interest. This represents a major advantage over the accepted gas chromatograph mass spectrometer (GCMS) technique for measuring gas concentrations and isotope ratios. The careful and extensive gas purification procedures required to remove impurities for reliable GCMS measurements will not be required for an IR laser gas analysis. The infrared laser gas analysis technique is being developed to measure stable isotopic ratios of gases such as CO2, CH4, N2O, and NH3. This will eventually lead to development of instruments capable of in situ istopic measurements on planets such as Mars. The carbon (C-12, C-13) isotope ratio is indicative of the type of carbon fixation mechanisms (e.g., photosynthesis, respiration) in operation on a planet, while the nitrogen (N-14, N-15) isotope ratio can probably be used to date nitrogen-bearing Martian samples. The absorbance ratio of two adjacent lines of CO2 in the 2300/cm (4.3 micron) region of the spectrum was measured. The precision of the measurement is presently better than 1 percent and significant improvement is anticipated as rapid sweep-integration techniques and computer controlled data acquistion capabilities are incorporated.

Becker, J. F.↗
NASA NTRS1994

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↗
NASA NTRS1995

Infrared Spectroscopy of Matrix-Isolated Polycyclic Aromatic Hydrocarbon Cations. 3. The Polyacenes Anthracene, Tetracene, and Pentacene

Gaseous, ionized Polycyclic Aromatic Hydrocarbons (PAH's) are thought to be responsible for a very common family of interstellar infrared emission bands. Unfortunately, very little infrared spectroscopic data are available on ionized PAH's. Here we present the near- and mid-infrared spectra of the polyacene cations anthracene, tetracene, and pentacene. We also report the vibrational frequencies and relative intensities of the pentacene anion. The cation bands corresponding to the CC modes are typically about 10-20 times more intense than those of the CH out-of-plane bending vibrations. For the cations the CC stretching and CH in-plane bending modes give rise to bands which are an order of magnitude stronger than for the neutral species, and the CH out-of-plane bends produce bands which are 3-20 times weaker than in the neutral species. This behavior is similar to that found for most other PAH cations. The most intense PAH cation bands fall within the envelopes of the most intense interstellar features. The strongest absorptions in the polyacenes anthracene, tetracene, and pentacene tend to group around 1400 / cm (between about 1340 and 1500 / cm) and near 1180 /cm, regions of only moderate interstellar emission. These very strong polyacene bands tend to fall in gaps in the spectra of the other PAH cations studied to date suggesting that while PAHs with polyacene structures may contribute to specific regions of the interstellar emission spectra, they are not dominant members of the interstellar PAH family.

Hudgins, D. M.↗
NASA NTRS2010

Subframe Burst Gating for Raman Spectroscopy in Combustion

We describe an architecture for spontaneous Raman scattering utilizing a frame-transfer CCD sensor operating in a subframe burst-gating mode to realize time-resolved combustion diagnostics. The technique permits all-electronic optical gating with microsecond shutter speeds 5 J.Ls) without compromising optical throughput or image fidelity. When used in conjunction with a pair of orthogonally polarized excitation lasers, the technique measures single-shot vibrational Raman scattering that is minimally contaminated by problematic optical background noise.

Kojima, Jun↗
NASA NTRS1990

The photoelectron spectroscopy of ZnCl2

The ionization energies (IEs) corresponding to the Cl ligand electrons and the Zn 3d electrons in ZnCl2, computed using large Gaussian basis sets and a high level of correlation treatment, are presented. The IEs for the Cl ligand electrons are in excellent agreement with those determined from photoelectron spectra. The IEs corresponding to the Zn 3d electrons agree with experiment relatively well in absolute magnitude, but differ in order. The vibrational frequencies of the ground state agree very well with experiment, and predictions are made for the corresponding frequencies in the positive ion.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2003

A Study of Olivine Alteration to Iddingsite Using Raman Spectroscopy

A crucial task of Mars surface science is to determine past environmental conditions, especially aqueous environments and their nature. Identification of mineral alteration by water is one way to do this. Recent work interprets TES spectra as indicating altered basalt on Mars. Olivine, a primary basaltic mineral, is easily altered by aqueous solutions. Alteration assemblages of olivine may be specific to deuteric, hydrothermal, surface water, or metamorphic environments. Raman spectra are produced by molecular vibrations and provide direct means for studying and identifying alteration products. Here, we present a combined study of changes in the chemical composition and Raman spectra of an olivine as it alters to iddingsite. Iddingsite is found in some SNC meteorites and is presumably present on Mars. The term 'iddingsite' has been used as a catch-all term to describe reddish alteration products of olivine, although some authors ascribe a narrower definition: an angstrom-scale intergrowth of goethite and smectite (presumably saponite) formed in an oxidizing and fluid-rich environment. Alteration conserves Fe (albeit oxidized) but requires addition of Al and H2O and removal of Mg and Si. The smectite that forms may be removed by continued alteration. Dehydration of the goethite forms hematite. Our purpose is to study the mineral assemblage, determine the structural and chemical variability of the components with respect to the degree of alteration, and to find spectral indicators of alteration that will be useful during in-situ analyses on Mars.

Kuebler, K. E.↗
NASA NTRS2005

Precise Laboratory Measurement of Line Frequencies Useful to Studies of Star and Planet Formation

In March 2002, we began a program in laboratory spectroscopy to provide accurate molecular line frequencies essential to studies of the motions and abundance in star-forming dense cores and planet-forming circumstellar disks. Summarized here is the progress that has been made in Year 3 of this grant. Work included measurement of 10 successive rotational lines in the ground vibrational state of SiO between 86 and 500 GHz, and two lines near 800 GHz to an accuracy of a few kHz; conducting pilot experiments on molecular ions in collision-free supersonic beams, including HCO+, N2H+, and H2D+; measurement of 22 lines of CN between 113 and 340 GHz; and setting up an experiment that would allow us to refine earlier measurements of the neutral species such as C3H2, CCS, H2CS, and SO by observing the very narrow sub-Doppler (Lamb dip) features in the millimeter-wave spectra of these species.

Myers, Philip C.↗
NASA NTRS2012

Interference-free optical detection for Raman spectroscopy

An architecture for spontaneous Raman scattering (SRS) that utilizes a frame-transfer charge-coupled device (CCD) sensor operating in a subframe burst gating mode to realize time-resolved combustion diagnostics is disclosed. The technique permits all-electronic optical gating with microsecond shutter speeds (<5 .mu.s), without compromising optical throughput or image fidelity. When used in conjunction with a pair of orthogonally-polarized excitation lasers, the technique measures time-resolved vibrational Raman scattering that is minimally contaminated by problematic optical background noise.

Nguyen, Quang-Viet↗
NASA NTRS1980

Predicting the thermal/structural performance of the atmospheric trace molecules spectroscopy /ATMOS/ Fourier transform spectrometer

ATMOS is a Fourier transform spectrometer to measure atmospheric trace molecules over a spectral range of 2-16 microns. Assessment of the system performance of ATMOS includes evaluations of optical system errors induced by thermal and structural effects. In order to assess the optical system errors induced from thermal and structural effects, error budgets are assembled during system engineering tasks and line of sight and wavefront deformations predictions (using operational thermal and vibration environments and computer models) are subsequently compared to the error budgets. This paper discusses the thermal/structural error budgets, modelling and analysis methods used to predict thermal/structural induced errors and the comparisons that show that predictions are within the error budgets.

Miller, J. M.↗
NASA NTRS1974

Laser photoluminescence spectroscopy of photodissociation fragments

Laser induced photoluminescence spectroscopy has been used to study the energy partitioning among CN fragments produced by the photodissociation of C2N2. The CN radicals are produced in both the A 2Pi and the X 2Sigma+ states. The A state is formed primarily in the nu-prime = 0 level, and the X state is formed in the lower vibrational levels. Since the photodissociation process does not produce the maximum amount of vibrational excitation in the CN fragments, it is suggested that the excess energy goes into either translational and/or rotational excitation of the CN.

Jackson, W. M.↗
NASA NTRS1989

F.T. spectroscopy of OH produced in a microwave surface plasma

Emission spectra of the hydroxyl radical have been recorded between 450 and 4200/cm at 0.0027/cm unapodized resolution from an air+oxygen+water vapor plasma, using a surface microwave discharge. The characteristics of the source are described. The emission spectra were recorded with the F.T. spectrometer using a GeCu detector and KCl beams plitter. High J values were observed both for the pure rotational transition in v=0 and v=1 vibrational levels, and for the rovibrational transition in the 0-1 and 1-2 bands. The set of line intensity data will be used to compute the electric dipole moment function of OH.

Benidar, A.↗
NASA NTRS1998

In Situ Infrared Spectroscopy of the Gaseous Species Present in a Diamond Chemical Vapor Deposition System

We interfaced a Hot-Filament Chemical Vapor Deposition (HFCVD) system to the emission port of an FT-IR spectrometer, in order to study the gas phase species present during the deposition of diamond thin films. The implementation of the infrared (IR) emission technique in situ allowed the study of various carbon-containing species believed to be crucial in diamond film growth. The two IR-active vibrational fundamentals of methane, v(3)(f2) and v(4)(f2), were observed at three different filament temperatures: 1000, 1500 and 2000 C. However, the net signal of v(3) was emission, while that of v(4) was absorption. These results indicate that the v(4) fundamental is excited beyond equilibrium, while the v(3) fundamental remains mostly in the ground state. This is due to the small concentration of methane, the low energy of v(4) compared to v(3) or to the Hz vibrational mode, and symmetry considerations that forbid interaction among the four fundamentals of methane. Thus, the excitation of v(3) is more likely than its decay under HFCVD conditions, producing a non-equilibrium population. At a filament temperature of 2000 C, the v(3) (sigma(+)(3)) fundamental of acetylene and a band at 1328 cm-l also ascribed to acetylene (v5 (pi(U)) + v4) appear in net absorption. This correlates well with the onset of molecular hydrogen breaking by the filament, which occurs at temperatures around 2000 C and above. The hydrogen atoms produced in this heterogeneous reaction give rise to a chain of reactions that lead to acetylene, among other carbonaceous species.

Morell, G.↗
NASA NTRS1988

Measurements of the ClO radical vibrational band intensity and the ClO + ClO + M reaction product

There is considerable interest in the kinetics and concentrations of free radicals in the stratosphere. Chlorine monoxide is a critically important radical because of its role in catalytic cycles for ozone depletion. Depletion occurs under a wide variety of conditions including the Antarctic spring when unusual mechanisms such as the BrO sub x/ClO sub x, ClO dimer (Cl sub 2 O sub 2), and ClO sub x/HO sub x cycles are suggested to operate. Infrared spectroscopy is one of the methods used to measure ClO in the stratosphere (Menzies 1979 and 1983; Mumma et al., 1983). To aid the quantification of such infrared measurements, researchers measured the ClO ground state fundamental band intensity.

Burkholder, James B.↗
NASA NTRS1985

Theoretical calculation of ozone vibrational infrared intensities

An ab initio dipole moment function for ozone has been computed using the CASSCF (complete active space self-consistent field) method, and forms the basis for a calculation of ozone infrared band intensities. Vibrational wave functions were generated using the variational method with potential energy surfaces derived from experimental force constants. Computed values of the permanent dipole moment, dipole moment derivatives, and infrared band strengths are all found to be in remarkably good agreement with experiment. Intensities are predicted for hot bands for which experimental values are unavailable, and implications for atmospheric ozone spectroscopy are discussed. As the dipole moment matrix element signs are now established for nearly all of the observed bands, further refinement of the dipole moment function is possible.

Adler-Golden, S. M.↗
NASA NTRS1991

Nonequilibrium in a low power arcjet nozzle

Emission spectroscopy measurements were made of the plasma flow inside the nozzle of a 1 kW class arcjet thruster. The thruster propellant was a hydrogen-nitrogen mixture used to simulate fully decomposed hydrazine. The 0.25 mm diameter holes were drilled into the diverging section of the tungsten thruster nozzle to provide optical access to the internal flow. Atomic electron excitation, vibrational, and rotational temperatures were determined for the expanding plasma using relative line intensity techniques. The atomic excitation temperatures decreased from 18,000K at a location 3 mm downstream of the constrictor to 9,000K at a location 9 mm from the constrictor, while the molecular vibrational and rotational temperatures decreased from 6,500K to 2,500K and from 8,000K to 3,000K, respectively, between the same locations. The electron density measured using hydrogen H line Stark broadening decreased from about 10(exp 15) cm(-3) to about 2 times 10(exp 14) cm(-3) during the expansion. The results show that the plasma is highly nonequilibrium throughout the nozzle, with most relaxation times equal or exceeding the particle residence time.

Zube, Dieter M.↗