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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.

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At least 109 records · Page 6
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NASA NTRS1985

Molecular orbital predictions of the vibrational frequencies of some molecular ions

The initial detections of IR vibration-rotation bands in polyatomic molecular ions by recent spectroscopic advances were guided by ab initio prediction of vibrational frequencies. The present calculations predict the vibrational frequencies of additional ions which are candidates for laboratory analysis. Neutral molecule vibrational frequencies were computed at three levels of theory and then compared with experimental data; the effect of scaling was also investigated, in order to determine how accurately vibrational frequencies could be predicted. For 92 percent of the frequencies examined, the relatively simple HF/6-31G theory's vibrational frequencies were within 100/cm of experimental values, with a mean absolute error of 49/cm. On this basis, the frequencies of 30 molecular ions (many possessing astrophysical significance) were computed.

Defrees, D. J.↗
NASA NTRS1986

Multi-level study of C3H2: The first interstellar hydrocarbon ring

Cyclic species in the interstellar medium have been searched for almost since the first detection of interstellar polyatomic molecules. Eleven different C3H2 rotational transitions were detected; 9 of which were studied in TMC-1, a nearby dark dust cloud, are shown. The 1 sub 10 yields 1 sub 01 and 2 sub 20 yields 2 sub 11 transitions were observed with the 43 m NRAO telescope, while the remaining transitions were detected with the 14 m antenna of the Five College Radio Observatory (FCRAO). The lines detected in TMC-1 have energies above the ground state ranging from 0.9 to 17.1 K and consist of both ortho and para species. Limited maps were made along the ridge for several of the transitions. The HC3N J = 2 yields 1 transition were mapped simultaneously with the C3H2 1 sub 10 yields 1 sub 01 line and therefore can compare the distribution of this ring with a carbon chain in TMC-1. C3H2 is distributed along a narrow ridge with a SE - NW extension which is slightly more extended than the HC2N J = 2 yields 1. Gaussian fits gives a FWHP extension of 8'5 for C3H2 while HC3N has a FWHP of 7'. The data show variations of the two velocity components along the ridge as a function of transition. Most of the transitions show a peak at the position of strongest HC3N emission while the 2 sub 21 yields 2 sub 10 transition shows a peak at the NH3 position.

Madden, S. C.↗
NASA NTRS1986

Two-photon laser-induced fluorescence detection of OH

The TP-LIF OH sensor is based on the principle that a molecule having multiple energy states, all of which are bonding, can be pumped into the highest state with the resulting fluorescence being blue-shifted relative to all pumping wavelengths. In this way, one can successfully discriminate against virtually all noise sources in the system using long wavelength blocking filters in conjunction with solar-blind photomultiplier tubes. Thus, these systems tend to be signal limited rather than signal-to-noise limited as is true of the SP-LIF technique as well as other conventional analytical methods. The trick to achieving the above sampling scheme, with high efficiency, is in the use of high photon fluxes of short time duration. Obviously, the latter type of light source is fulfilled nicely by available pulsed lasers. From an operational point of view, however, this laser source needs to be tunable. The latter characteristic permits extremely high selectivity for the detection of a diatomic or simple polyatomic molecule by taking advantage of the high-resolution spectroscopic features of these type species.

Davis, D. D.↗
NASA NTRS1986

Ultrasensitive detection of atmospheric trace gases using frequency modulation spectroscopy

Frequency modulation (FM) spectroscopy is a new technique that promises to significantly extend the state-of-the-art in point detection of atmospheric trace gases. FM spectroscopy is essentially a balanced bridge optical heterodyne approach in which a small optical absorption or dispersion from an atomic or molecular species of interest generates an easily detected radio frequency (RF) signal. This signal can be monitored using standard RF signal processing techniques and is, in principle, limited only by the shot noise generated in the photodetector by the laser source employed. The use of very high modulation frequencies which exceed the spectral width of the probed absorption line distinguishes this technique from the well-known derivative spectroscopy which makes use of low (kHz) modulation frequencies. FM spectroscopy was recently extended to the 10 micron infrared (IR) spectral region where numerous polyatomic molecules exhibit characteristic vibrational-rotational bands. In conjunction with tunable semiconductor diode lasers, the quantum-noise-limited sensitivity of the technique should allow for the detection of absorptions as small as .00000001 in the IR spectral region. This sensitivity would allow for the detection of H2O2 at concentrations as low as 1 pptv with an integration time of 10 seconds.

Cooper, David E.↗
NASA NTRS1986

Carbon monoxide in cometary ice

Carbon monoxide has been positively identified by means of ultraviolet fluorescence in the Fourth Positive System in two comets, West (1976 VI) and Bradfield (1979 X). In both cases, the spatial distribution of the emission is consistent with the CO being a 'parent' molecule, present in the cometary ice, rather than a dissociation product of a polyatomic species such as CO2 or HCOH. However, the abundance of CO relative to that of H2O is more than an order of magnitude smaller for comet Bradfield than for comet West. Further data on CO are expected with the use of more sensitive ultraviolet instruments such as the ASTRO spectrographs which will observe P/Halley in March 1986.

Feldman, P. D.↗
NASA NTRS1986

Picosecond coherent anti-Stokes Raman scattering (CARS) study of vibrational dephasing of carbon disulfide and benzene in solution

The vibrational dephasing of the 656/cm mode (nu1, a1g) of CS2 and the 991/cm mode (nu2, a1g) of benzene have been studied as a function of concentration in mixtures with a number of solvents using a ps time-resolved CARS technique. This technique employs two tunable synchronously-pumped mode-locked dye lasers in a stimulated Raman pump, coherent anti-Stokes Raman probe time-resolved experiment. Results are obtained for CS2 in carbon tetrachloride, benzene, nitrobenzene, and ethanol and for benzene nu2 in CS2. The dephasing rates of CS2 nu1 increase on dilution with the polar solvents and decrease or remain constant on dilution with the nonpolar solvents. The CS2/benzene solutions show a contrasting behavior, with the CS2 nu1 dephasing rate being nearly independent of concentration whereas the benzene nu2 dephasing rate decreases on dilution. These results are compared to theoretical models for vibrational dephasing of polyatomic molecules in solution.

Perry, Joseph W.↗
NASA NTRS1987

Climate-chemical interactions and effects of changing atmospheric trace gases

The paper considers trace gas-climate effects including the greenhouse effect of polyatomic trace gases, the nature of the radiative-chemical interactions, and radiative-dynamical interactions in the stratosphere, and the role of these effects in governing stratospheric climate change. Special consideration is given to recent developments in the investigations of the role of oceans in governing the transient climate responses, and a time-dependent estimate of the potential trace gas warming from the preindustrial era to the early 21st century. The importance of interacting modeling and observational efforts is emphasized. One of the problems remaining on the observational front is the lack of certainty in current estimates of the rate of growth of CO, O3, and NOx; the primary challenge is the design of a strategy that will minimize the sampling errors.

Ramanathan, V.↗
NASA NTRS1988

The violet and ultraviolet opacity problem for carbon stars

The paper considers the longstanding problem of the 'violet opacity' in cool carbon stars by testing, through synthetic spectra, many new and previously suggested opacity sources, based on currently available model atmospheres for carbon stars and M giant stars. While several bound-free edges of neutral metals are important opacity sources, those of Na I at at 2413 A, Mg I at 2514 A, and particularly Ca I at 2940 A are especially significant. Collectively, thousands of atomic lines are important, and the enormous line of Mg I at 2852 A influences the spectrum well into the visible. The pseudocontinuum of C3 and the photoionization continuum of CH both play noticeable but secondary roles. Synthetic spectra form the carbon star models with and without polyatomic molecules fit nicely the collected observations of the well-observed carbon star TX Psc.

Johnson, Hollis R.↗
NASA NTRS1989

New emission features in the 11-13 micron region and their relationship to polycyclic aromatic hydrocarbons

Moderate-resolution spectra of NGC 7027, HD 44179, IRAS 2182+5050, and BD +30 deg 3639 are presented, showing that the 11.3-micron feature actually peaks at 11.22 microns. Evidence is found for new emission features near 11.9 and 12.7 microns, supporting an origin from PAHs. Also, the observed asymmetry of the 11.3-micron band is consistent with the anharmonicity expected in the C-H out-of-plane bending mode in PAHs. The analysis of the 11-13-micron emission suggests that the molecular structures of the most intensely emitting free PAHs vary between the high-excitation environment in NGC 7027 and the low-excitation but high-flux environment close to HD 44179. In addition, a series of regularly spaced features between 10 and 11 microns is detected in the spectrum of HD 44179, suggesting that a simple polyatomic hydride is present in the object's gas phase.

Witteborn, F. C.↗
NASA NTRS1990

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.↗
NASA NTRS1990

Theoretical investigation of gas-surface interactions

A Dirac-Hartree-Fock code was developed for polyatomic molecules. The program uses integrals over symmetry-adapted real spherical harmonic Gaussian basis functions generated by a modification of the MOLECULE integrals program. A single Gaussian function is used for the nuclear charge distribution, to ensure proper boundary conditions at the nuclei. The Gaussian primitive functions are chosen to satisfy the kinetic balance condition. However, contracted functions which do not necessarily satisfy this condition may be used. The Fock matrix is constructed in the scalar basis and transformed to a jj-coupled 2-spinor basis before diagonalization. The program was tested against numerical results for atoms with a Gaussian nucleus and diatomic molecules with point nuclei. The energies converge on the numerical values as the basis set size is increased. Full use of molecular symmetry (restricted to D sub 2h and subgroups) is yet to be implemented.

Dyall, Kenneth G.↗
NASA NTRS1990

Analytical modeling of nonradial expansion plumes

The 'Modified Simons' model presented allows the nonradial nature of axisymmetric rocket and thruster plume flowfields having a large exit Mach number and/or a large nozzle exit half-angle to be successfully predicted. The model is applied to monatomic and polyatomic gas (N, Ar, tetrafluoromethane) expansions; the nonradial density decay observed experimentally is successfully predicted.

Boyd, Iain D.↗
NASA NTRS1990

Deuterium enrichment in the primitive ices of the protosolar nebula

On the basis of CH3D/CH4-ratio observations in the outer planets, the present effort to estimate the D/H ratio of the protosolar nebula's primitive ices arrives at two simple, yet effectively limiting models which constrain the degree of dilution undergone by deuterated volatiles through mixing with the initial hydrogen envelopes. These volatiles would have been contributed to planetary atmospheres by evaporated primordial ices. Ice D/H ratio model results of 0.0001 to 0.001 are compared with values for other potentially primitive material-containing bodies in the solar system, as well as with D/H ratio values from interstellar polyatomic molecules.

Lutz, Barry L.↗
NASA NTRS1991

New approach in direct-simulation of gas mixtures

Results are reported for an investigation of a new direct-simulation Monte Carlo method by which energy transfer and chemical reactions are calculated. The new method, which reduces to the variable cross-section hard sphere model as a special case, allows different viscosity-temperature exponents for each species in a gas mixture when combined with a modified Larsen-Borgnakke phenomenological model. This removes the most serious limitation of the usefulness of the model for engineering simulations. The necessary kinetic theory for the application of the new method to mixtures of monatomic or polyatomic gases is presented, including gas mixtures involving chemical reactions. Calculations are made for the relaxation of a diatomic gas mixture, a plane shock wave in a gas mixture, and a chemically reacting gas flow along the stagnation streamline in front of a hypersonic vehicle. Calculated results show that the introduction of different molecular interactions for each species in a gas mixture produces significant differences in comparison with a common molecular interaction for all species in the mixture. This effect should not be neglected for accurate DSMC simulations in an engineering context.

Chung, Chan-Hong↗
NASA NTRS1992

Theoretical investigation of gas-surface interactions

The investigation into the appearance of intruder states from the negative continuum when some of the two-electron integrals were omitted was completed. The work shows that, provided all integrals involving core contracted functions in an atomic general contraction are included, or that the core functions are radially localized, meaningful results are obtained and intruder states do not appear. In the area of program development, the Dirac-Hartree-Fock (DHF) program for closed-shell polyatomic molecules was extended to permit Kramers-restricted open-shell DHF calculations with one electron in an open shell or one hole in a closed shell, or state-averaged DHF calculations over several particle or hole doublet states. One application of the open-shell code was to the KO molecule. Another major area of program development is the transformation of integrals from the scalar basis in which they are generated to the 2-spinor basis employed in parts of the DHF program, and hence to supermatrix form. Particularly concerning the omission of small component integrals, and with increase in availability of disk space, it is now possible to consider transforming the integrals. The use of ordered integrals, either in the scalar basis or in the 2-spinor basis, would considerably speed up the construction of the Fock matrix, and even more so if supermatrices were constructed. A considerable amount of effort was spent on analyzing the integral ordering and tranformation for the DHF program. The work of assessing the reliability of the relativistic effective core potentials (RECPs) was continued with calculation of the group IV monoxides. The perturbation of the metal atom provided by oxygen is expected to be larger than that provided by hydrogen and thus provide a better test of the qualification of the RECPs. Calculations on some platinum hydrides were carried out at nonrelativistic (NR), perturbation theory (PT) and DHF levels. Reprints of four papers describing this work are included.

Dyall, Kenneth G.↗
NASA NTRS1992

Computer program for calculating and fitting thermodynamic functions

A computer program is described which (1) calculates thermodynamic functions (heat capacity, enthalpy, entropy, and free energy) for several optional forms of the partition function, (2) fits these functions to empirical equations by means of a least-squares fit, and (3) calculates, as a function of temperture, heats of formation and equilibrium constants. The program provides several methods for calculating ideal gas properties. For monatomic gases, three methods are given which differ in the technique used for truncating the partition function. For diatomic and polyatomic molecules, five methods are given which differ in the corrections to the rigid-rotator harmonic-oscillator approximation. A method for estimating thermodynamic functions for some species is also given.

Mcbride, Bonnie J.↗
NASA NTRS1993

Pseudospectral simulation of compressible turbulence using logarithmic variables

The direct numerical simulation of dissipative, highly compressible turbulent flow is performed using a pseudospectral Fourier technique. The governing equations are cast in a form where the important physical variables are the fluid velocity and the natural logarithms of the fluid density and temperature. Bulk viscosity is utilized to model polyatomic gases more accurately and to ensure numerical stability in the presence of strong shocks. Numerical examples include three-dimensional supersonic homogeneous turbulence and two-dimensional shock-turbulence interactions.

Shebalin, John V.↗
NASA NTRS1993

Laser diagnostics for small rockets

Two nonintrusive flowfield diagnostics based on spectrally-resolved elastic (Rayleigh) and inelastic (Raman) laser light scattering were developed for obtaining local flowfield measurements in low-thrust gaseous H2/O2 rocket engines. The objective is to provide an improved understanding of phenomena occurring in small chemical rockets in order to facilitate the development and validation of advanced computational fluid dynamics (CFD) models for analyzing engine performance. The laser Raman scattering diagnostic was developed to measure major polyatomic species number densities and rotational temperatures in the high-density flowfield region extending from the injector through the chamber throat. Initial application of the Raman scattering diagnostic provided O2 number density and rotational temperature measurements in the exit plane of a low area-ratio nozzle and in the combustion chamber of a two-dimensional, optically-accessible rocket engine. In the low-density nozzle exit plane region where the Raman signal is too weak, a Doppler-resolved laser Rayleigh scattering diagnostic was developed to obtain axial and radial mean gas velocities, and in certain cases, H2O translational temperature and number density. The results from these measurements were compared with theoretical predictions from the RPLUS CFD code for analyzing rocket engine performance. Initial conclusions indicate that a detailed and rigorous modeling of the injector is required in order to make direct comparisons between laser diagnostic measurements and CFD predictions at the local level.

Zupanc, Frank J.↗