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At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Characterization of silicon-carbon clusters by infrared laser spectroscopy. The nu 1 band of SiC4

The nu 1 fundamental vibration of linear SiC4 has been observed by infrared diode laser spectroscopy of a supersonic cluster beam. Twenty-four rovibrational transitions were measured in the spectral region of 2094.6 to 2097.1 cm-1, the rotational temperature was 10 K. A combined least-squares fit of these transitions with previously reported microwave data yielded the following molecular constants: nu 1 = 2095.45806(37) cm-1, B" = 0.051161131(52) cm-1, and B' = 0.0509157(96) cm-1. These results are compared to vibrational spectroscopy measurements of SiC4 trapped in a solid Ar matrix and to ab initio calculations.

NASA Discipline Exobiology↗
NASA NTRS1978

Infrared vibration-rotation spectra of the ClO radical using tunable diode laser spectroscopy

Tunable diode laser spectroscopy is used to measure the infrared vibration-rotation spectra of the ClO radical. The radical is generated in a flow system where a Cl2-He mixture passes through a microwave discharge to dissociate the Cl2. An O3-O2 mixture from an ozone generator is injected into the system downstream of the microwave discharge where O3 combines with Cl to form ClO. By adjusting the gas flow rates to yield an excess of Cl atoms, all the ozone is combined. ClO concentration is measured with UV absorption at 2577 and 2772 A and a deuterium lamp as a continuous source. Total cell pressure is 5.5 torr. The diode laser spectrometer is calibrated with ammonia lines as a reference where possible. The frequency of vibration-rotation lines is expressed as a function of rotational quantum number, fundamental vibrational frequency, and the rotational constants of the upper and lower vibrational states.

Rogowski, R. S.↗
NASA NTRS2001

Ab Initio and Improved Empirical Potentials for the Calculation of the Anharmonic Vibrational States and Intramolecular Mode Coupling of N-Methylacetamide

The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have important implications for the anharmonic force fields of peptides, for which N-methylacetamide is a model.

Gregurick, Susan K.↗
NASA NTRS2006

A Brief Summary of Some of the Laboratory Astrophysics Workshop

Our present knowledge of the molecular universe has come primarily from radio observations [ I include here millimeter and submillimeter in this rubric]. There are a number of reasons for this but the primary one is the extremely high spectral resolution. The ease of observing emission from the volume of dense molecular clouds without significant attenuation by scattering from dust has shown this to be the powerful observational tool for molecular astronomy. Finally the relative simplicity of rotational compared to vibrational or electronic spectroscopy allows carrier identification as well as facile evaluation of cloud conditions such as density and temperature. These virtues become tenuous as the astronomical observations are pushed to higher frequencies for enhanced observational sensitivity. Thus precision rest frequencies are mandatory for the search for new species. We may inquire about which new species require particular attention, and which species may be relatively safely predicted on the basis of lower frequency laboratory measurements. For a rigid rotor the three rotational constants are sufficient to completely specify the transition frequencies. The intensities require the three components of the electric dipole moment. For semirigid species, where the centrifugal distortion, may be treated at the quartic level of angular momentum (Bunker et al. 1998), up to five additional constants are required (Watson 1967). There are a number of such species of considerable interest, where laboratory measurements are adequate for astronomical searches.

Klemperer, William↗
NASA NTRS1980

Atmospheric quenching of vibrationally excited O2/1 Delta/

The paper presents photolysis absorption spectroscopy experimental results which show rapid vibrational quenching of O2(1 Delta, v not less than 1) molecular oxygen fragments in an atmospheric environment. The reactions of this species were determined by flash photolysis of ozone in the Hartley band combined with absorption spectroscopic detection of O2(1 Delta v equals 0) fragments and resonance fluorescence detection of O(3P). It was shown that rapid vibrational deactivation occurs under atmospheric conditions; in addition, an upper limit was determined for the photolytic channel of the O(1D) + O3 yields O2(1 Sigma) reaction.

Klais, O.↗
NASA NTRS1981

Temperature profiles of inhibited flames using Raman spectroscopy

Laser Raman scattering from vibrational and rotational states of N2 and H2 has been used to determine temperature profiles for several H2/O2/N2 flames with and without HBr present. The inhibiting effect of HBr is clearly demonstrated and the derived properties of burning velocity and inhibition index are in good agreement with previous experimental measurements and theoretical calculations.

Drake, M. C.↗
NASA NTRS1991

The study of molecular spectroscopy by ab initio methods

This review illustrates the potential of theory for solving spectroscopic problems. The accuracy of approximate techniques for including electron correlation have been calibrated by comparison with full configuration-interaction calculations. Examples of the application of ab initio calculations to vibrational, rotational, and electronic spectroscopy are given. It is shown that the state-averaged, complete active space self-consistent field, multireference configuration-interaction procedure provides a good approach for treating several electronic states accurately in a common molecular orbital basis.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2006

THz Spectroscopy and Spectroscopic Database for Astrophysics

Molecule specific astronomical observations rely on precisely determined laboratory molecular data for interpretation. The Herschel Heterodyne Instrument for Far Infrared, a suite of SOFIA instruments, and ALMA are each well placed to expose the limitations of available molecular physics data and spectral line catalogs. Herschel and SOFIA will observe in high spectral resolution over the entire far infrared range. Accurate data to previously unimagined frequencies including infrared ro-vibrational and ro-torsional bands will be required for interpretation of the observations. Planned ALMA observations with a very small beam will reveal weaker emission features requiring accurate knowledge of higher quantum numbers and additional vibrational states. Historically, laboratory spectroscopy has been at the front of submillimeter technology development, but now astronomical receivers have an enormous capability advantage. Additionally, rotational spectroscopy is a relatively mature field attracting little interest from students and funding agencies. Molecular data base maintenance is tedious and difficult to justify as research. This severely limits funding opportunities even though data bases require the same level of expertise as research. We report the application of some relatively new receiver technology into a simple solid state THz spectrometer that has the performance required to collect the laboratory data required by astronomical observations. Further detail on the lack of preparation for upcoming missions by the JPL spectral line catalog is given.

Pearson, John C.↗
NASA NTRS2006

THz Spectroscopy and Spectroscopic Database for Astrophysics

Molecule specific astronomical observations rely on precisely determined laboratory molecular data for interpretation. The Herschel Heterodyne Instrument for Far Infrared, a suite of SOFIA instruments, and ALMA are each well placed to expose the limitations of available molecular physics data and spectral line catalogs. Herschel and SOFIA will observe in high spectral resolution over the entire far infrared range. Accurate data to previously unimagined frequencies including infrared ro-vibrational and ro-torsional bands will be required for interpretation of the observations. Planned ALMA observations with a very small beam will reveal weaker emission features requiring accurate knowledge of higher quantum numbers and additional vibrational states. Historically, laboratory spectroscopy has been at the front of submillimeter technology development, but now astronomical receivers have an enormous capability advantage. Additionally, rotational spectroscopy is a relatively mature field attracting little interest from students and funding agencies. Molecular database maintenance is tedious and difficult to justify as research. This severely limits funding opportunities even though data bases require the same level of expertise as research. We report the application of some relatively new receiver technology into a simple solid state THz spectrometer that has the performance required to collect the laboratory data required by astronomical observations. Further detail on the lack of preparation for upcoming missions by the JPL spectral line catalog is given.

THz spectrometer↗
NASA NTRS1982

Compensation mechanism in liquid encapsulated Czochralski GaAs Importance of melt stoichiometry

It is shown that the key to reproducible growth of undoped semi-insulating GaAs by the liquid encapsulated Czochralski (LEC) technique is the control over the melt stoichiometry. Twelve crystals were grown from stoichiometric and nonstoichiometric melts. The material was characterized by secondary ion mass spectrometry, localized vibrational mode far infrared spectroscopy, Hall-effect measurements, optical absorption, and photoluminescence. A quantitative model for the compensation mechanism in the semi-insulating material was developed based on these measurements. The free carrier concentration is controlled by the balance between EL2 deep donors and carbon acceptors; furthermore, the incorporation of EL2 is controlled by the melt stoichiometry, increasing as the As atom fraction in the melt increases. As a result, semi-insulating material can be grown only from melts above a critical As composition. The practical significance of these results is discussed in terms of achieving high yield and reproducibility in the crystal growth process.

Holmes, D. E.↗
NASA NTRS1999

Fourier Transform Ultraviolet Spectroscopy of the A Pi-2(3/2) Direct Current X Pi-2(3/2) Transition of BrO

The first spectra of the A (2)Pi(sub 3/2) from X (2)Pi(sub 3/2) electronic transition of BrO using Fourier transform ultraviolet spectroscopy are obtained. Broadband vibrational spectra acquired at 298 +/- 2 K and 228 +/- 5 K, as well as high-resolution rotational spectra of the A from X 7,0 and 12,0 vibrational bands are presented. Wavenumber positions for the spectra are obtained with high accuracy, and cross section assignments are made, incorporating the existing literature. With 35 cm(exp -1) (0.40 nm) resolution the absolute cross section at the peak of the 7,0 band is determined to be (1.58 +/- 0.12) x 10(exp -17) sq cm/molecule at 298 +/- 2 K and (1.97 +/- 0.15) x 10(exp -17) sq cm/molecule at 228 +/- 5 K. BrO dissociation energies are determined with a graphical Birge-Sponer technique, using Le Roy-Bernstein theory to place an upper limit on the extrapolation. From the ground-state dissociation energy, D(sub o)" = 231.0 +/- 1.7 kJ/mol, the heat of formation of BrO(g) is calculated, del(sub f)H(0 K) = 133.7 +/- 1.7 kJ/mol and del(sub f)H(298.15 K) = 126.2 +/- 1.7 kJ/mol. Cross sections for the high-resolution 7,0 and 12,0 rotational peaks are the first to be reported. The band structures are modeled, and improved band origins, rotational constants, centrifugal distortion constants, and linewidths are determined. In particular, J-dependent linewidths and lifetimes are observed for the both the 7,0 and 12,0 bands.

Wilmouth, David M.↗
NASA NTRS2010

Raman Scattering in a New Carbon Material

Samples of a new carbon material, Diamonite-B, were fabricated under high pressure from a commercial carbon black--identified as mixed fullerenes. The new material is neither graphite-like nor diamond-like, but exhibits electrical properties close to graphite and mechanical properties close to diamond. The use of Raman spectroscopy to investigate the vibrational dynamics of this new carbon material and to provide structural characterization of its short-, medium- and long-range order is reported. We also provide the results of investigations of these samples by high-resolution electron microscopy and X-ray diffraction. Hardness, electrical conductivity, thermal conductivity and other properties of this new material are compared with synthetic graphite-like and diamond-like materials, two other phases of synthetic bulk carbon.

Voronov, O. A.↗
NASA NTRS2011

Interpreting Methanol v(sub 2)-Band Emission in Comets Using Empirical Fluorescence g-Factors

For many years we have been developing the ability, through high-resolution spectroscopy targeting ro-vibrational emission in the approximately 3 - 5 micrometer region, to quantify a suite of (approximately 10) parent volatiles in comets using quantum mechanical fluorescence models. Our efforts are ongoing and our latest includes methanol (CH3OH). This is unique among traditionally targeted species in having lacked sufficiently robust models for its symmetric (v(sub 3) band) and asymmetric (v(sub 2) and v(sub 9) bands) C-H3 stretching modes, required to provide accurate predicted intensities for individual spectral lines and hence rotational temperatures and production rates. This has provided the driver for undertaking a detailed empirical study of line intensities, and has led to substantial progress regarding our ability to interpret CH3OH in comets. The present study concentrates on the spectral region from approximately 2970 - 3010 per centimeter (3.367 - 3.322 micrometer), which is dominated by emission in the (v(sub 7) band of C2H6 and the v(sub 2) band of CH3OH, with minor contributions from CH3OH (v(sub 9) band), CH4 (v(sub 3)), and OH prompt emissions (v(sub 1) and v(sub 2)- v(sub 1)). Based on laboratory jet-cooled spectra (at a rotational temperature near 20 K)[1], we incorporated approximately 100 lines of the CH3OH v(sub 2) band, having known frequencies and lower state rotational energies, into our model. Line intensities were determined through comparison with several comets we observed with NIRSPEC at Keck 2, after removal of continuum and additional molecular emissions and correcting for atmospheric extinction. In addition to the above spectral region, NIRSPEC allows simultaneous sampling of the CH3OH v(sub 3) band (centered at 2844 per centimeter, or 3.516 micrometers and several hot bands of H2O in the approximately 2.85 - 2.9 micrometer region, at a nominal spectral resolving power of approximately 25,000 [2]. Empirical g-factors for v(sub 2) lines were based on the production rate as determined from the v(sub 3) Q-branch intensity; application to comets spanning a range of rotational temperatures (approximately 50 - 90 K) will be reported. This work represents an extension of that presented for comet 21P/Giacobini-Zinner at the 2010 Division for Planetary Sciences meeting [3]. Our empirical study also allows for quantifying CH3OH in comets using IR spectrometers for which the v(sub 3) and v(sub 2) bands are not sampled simultaneously, for example CSHELL/NASA IRTF or CRIRES/VLT.

DiSanti, Michael↗
NASA NTRS1990

Tunable far-IR laser spectroscopy of jet-cooled carbon clusters - The nu-2 bending vibration of C3

Seven rovibrational transitions of the (01/1/0)-(00/0/0) fundamental bending band of C3 have been measured with high precision with the use of a tunable far-infrared laser spectrometer. The C3 molecules were produced by laser vaporization of a graphite rod and cooled in a supersonic expansion. The astrophysically important nu-2 fundamental frequency is determined to be 63.416529(40)/cm. These measurements provide the basis for studies of C3 in the interstellar medium with far-infrared astronomy.

Schmuttenmaer, C. A.↗