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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1977

On the detection of newly created CN radicals and comets

Laboratory investigations of CN radical formation by photodissociation of parent molecules have suggested the possibility of observing emission lines in cometary spectra from newly formed CN radicals. These laboratory studies have shown that high initial internal excitation of CN is the rule with excitation of rotational levels N up to 70. In the collisionless environment of the cometary atmosphere this initial excitation would yield a corresponding distribution for the lowest vibrational level of the ground X(2) Sigma (+) state. Our calculations show that it is feasible with present observational techniques to detect photochemically excited lines with N approx. equal to 30 in the 0-0 band of the violet system.

Donn, B.↗
NASA NTRS1977

Theoretical study of the butadiynyl and cyanoethynyl radicals - Support for the identification of C3N in IRC + 10216

Quantum-mechanical calculations, using the matrix Hartree-Fock model, have been performed for the butadiynyl and cyanoethynyl radicals. A rotation constant of 4753 MHz is calculated for C4H, while for C3N the value 4955 MHz is obtained. These may be compared with the rotation constant of 4947.5 MHz derived from the recently observed doublets in the millimeter-wave spectrum of IRC + 10216, suggesting the cyanoethynyl radical as the carrier species of these lines. The electric dipole moment and hyperfine coupling constants of both species are predicted.

Wilson, S.↗
NASA NTRS1977

Laser induced photoluminiscence studies of primary photochemical production processes of cometary radicals

A tunable vacuum ultraviolet flash lamp was constructed. This unique flash lamp was coupled with a tunable dye laser detector and permits the experimenter to measure the production rates of ground state radicals as a function of wavelength. A new technique for producing fluorescent radicals was discovered. This technique called multiphoton ultraviolet photodissociation is currently being applied to several problems of both cometary and stratospheric interest. It was demonstrated that NO2 will dissociate to produce an excited fragment and the radiation can possibly be used for remote detection of this species.

Jackson, W. M.↗
NASA NTRS1978

Theoretical study of isocyanoacetylene and the isocyanoethynyl radical

Quantum mechanical calculations, using the matrix Hartree-Fock model, have been performed to obtain estimates of the rotation constants of the isocyanoacetylene molecule and the isocyanoethynyl radical which may be detectable in space. A rotation constant of 5076 MHz is calculated for HC2NC, while for the radical C2NC the value 5458 MHz is obtained.

Wilson, S.↗
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 NTRS1978

On the detection of newly created CN radicals in comets

A description is presented of laboratory measurements concerning the amount and the distribution of energy released into newly formed radicals by the photodissociation process. The experimental method used involved flash photolysis of the parent compound followed by laser induced fluorescence detection of the CN fragment. This method allowed the detection of individual rotational lines and, thereby, a monitoring of the relative populations of the vibrational-rotational levels of the CN ground state. The results obtained in the investigation suggest the possibility of observing emission lines in cometary spectra from newly formed CN radicals. Calculations show that it is feasible with present observational techniques to detect photochemically excited lines in the 0-0 band of the violet system.

Donn, B.↗
NASA NTRS1980

The fate of the hydroxyl radical in the earth's primitive atmosphere and implications for the production of molecular oxygen

Behavior of the hydroxyl radical produced by the photolysis of water vapor in the earth's early atmosphere is examined. Because of the substantial OH radical reactivity with trace species (CO, HCl, SO2, H2S, NH3, and CH4) the formation of molecular oxygen may be prevented, even at a trace species mixing ratio. The photolysis rate of H2O, with corrections for hydrogen exospheric escape, is capable of describing the oxidation of the atmosphere and crust but may not be used to determine the rate of molecular oxygen generation without consideration of the various OH-trace species reactions.

Vander Wood, T. B.↗
NASA NTRS1980

Laser spectroscopy of the CN radical and astrophysical applications

The formation of CN radicals by flash photolysis of a number of parent molecules was monitored by laser induced fluorescence in the B2Sigma(plus)-X2Sigma(plus) transition of CN. The rotational and vibrational energy of the newly formed radicals in the X state was measured directly. Formation of CN(A2Pi) in the lower vibrational levels was determined by an indirect method based on resonant energy transfer to higher vibrational levels of the ground state. These laboratory studies have shown that high initial internal excitation of CN with rotational levels of maximum N equals 50-70 is the rule. In general, the formation of simple molecules in excited states is commonly the case. There appear to be astrophysical systems where radiation from these excited levels may be detectable. Such observations would serve as a probe of molecular formation.

Cody, R. J.↗
NASA NTRS1981

Temperature dependence of the self-reaction of CH3O2 radicals

The rate constants for the reaction CH3O2 + CH3O2 yields products (1) were measured in the temperature range from 248 to 417 K, taking into consideration pressures in the range from 60 to 700 torr of N2. The experimental investigation was carried out in a Pyrex flash photolysis system employing ultraviolet absorption detection. Methylperoxy radicals (CH3O2) were produced by the photolysis of Cl2-CH4-O2 mixtures. Rate constants were measured by observing the second-order disappearance of CH3O2 radicals. Plots of 1/(CH3O2 optical density) vs. time were observed to be linear over a concentration change of a factor of 10-50. Results of the kinetic runs at each temperature are summarized in a table, and an Arrhenius plot of the data is shown in a graph.

Sander, S. P.↗
NASA NTRS1981

Calculation of activation energies for hydrogen-atom abstractions by radicals containing carbon triple bonds

Activation energies are calculated by the bond-energy-bond-order (BEBO) and the bond-strength-bond-length (BSBL) methods for the reactions of C2H radicals with H2, CH4, and C2H6 and for the reactions of CN radicals with H2 and CH4. The BSBL technique accurately predicts the activation energies for these reactions while the BEBO method yields energies averaging 9 kcal higher than those observed. A possible reason for the disagreement is considered.

Brown, R. L.↗
NASA NTRS1983

Relative rate constants for the reactions of atomic oxygen with HO2 anad OH radicals

Relative rate constants for the reactions O + HO2 - OH + O2 (1) and O + OH - H + O2 (2) were obtained by using the discharge-flow resonance fluorescence technique at 2 torr total pressure and 299 K. HO2 radicals were generated by reacting atomic hydrogen with an excess of O2. Quasi-steady-state concentrations of OH and HO2 were established in the presence of excess atomic oxygen. Observed concentration ratios, namely the ratio of the OH concentration to the HO2 concentration, resulted in a value of 1.7 + or 0.2 for k1/k2. The error limits are twice the standard deviation obtained from the data analysis. Overall experimental error is estimated to be + or - 25 percent. This result confirms earlier direct measurements of k1 and k2 which required knowledge of absolute radical or atomic oxygen concentrations.

Keyser, L. F.↗
NASA NTRS1984

Radical and ion molecule mechanisms in the polymerization of hydrocarbons and chlorosilanes in RF plasmas at low pressures ( 1.0 torr)

The ion-molecule and the radical-molecule mechanisms are responsible for the dissociation of hydrocarbons, and chlorosilane monomers and the formation of polymerized species, respectively, in the plasma state of a RF discharge. In the plasma, of a mixture of monomer with Ar, the rate determining step for both dissociation and polymerization is governed by an ion-molecular type interaction. Additions of H2 or NH3 to the monomer Ar(+) mixture transforms the rate determining step from an ion-molecular interaction to a radical-molecule type interaction for both monomer dissociation and polymerization processes.

Avni, R.↗
NASA NTRS1983

Vibration-rotation line strengths of the gas-phase OH radical

Absorption line strengths have been measured at 295 K for the first time for four vibration-rotation transitions of the OH radical, using a tunable, infrared diode-laser in conjunction with a molecular modulation spectrometer. A periodically varying OH concentration was created by photolysis, using a sinusoidally modulated 2537-A Hg lamp, of a flowing mixture of O3 and H2O contained within a quartz-walled White cell. The modulated absorption owing to the OH radical was subsequently observed by phase-sensitive detection. The absolute modulation amplitude of the OH number density was obtained by numerical simulation of the complete time-dependent photochemical system. The strongest transition measured was at 3407.607 kaysers, with a strength of 3.3 + or - 1.5 x 10 to the -20th per(cm molecule) sq cm.

Podolske, J.↗
NASA NTRS1984

Identification of the SiCC radical toward IC +10216 - The first molecular ring in an astronomical source

In the radio spectrum of the envelope of the evolved carbon star IRC +10216, the fraction of lines from exotic molecules seldom or never observed in the terrestrial laboratory is exceptionally high. At least 20 lines have not been identified, and it is not known whether one, two, or a number of new molecules are involved. It is shown in the present investigation that nine of the previously unidentified lines in IRC +10216 are produced by SiCC, a radical long known to exist in stellar atmospheres. The true ground-state geometry of this radical has only been obtained recently on the basis of an elegant two-photon ionization experiment in a supersonic molecular beam. Information regarding the molecular geometry and lower rotational levels of SiCC is presented in a graph. The intensities of the SiCC lines confirm the assignments, yield new data on the temperature and density in the envelope of IRC +10216, and indicate that the amount of SiCC there is substantial.

Thaddeus, P.↗
NASA NTRS1985

Stable polymeric carbon radicals. Part 2: Attempts at the preparation of polyradicals of the triphenylmethyl type linked by P-phenylene units

As starting materials for the preparation of polyradicals of triphenylmethyl type linked by p-phenylene units bis(4-iodophenylmethane) and bis(4-iodo-2,5-dimethyl-phenylmethane) were synthesized by a Sandmeyer reaction from the corresponding diamino compounds and subsequently transformed into the corresponding polymeric hydrocarbons 6a and 6b by an Ullmann condensation. In the following step 6a and 6b were brominated at the tert. carbon atom by means of N-bromosuccinimide. The reaction of the resulting poly (4,4'-biphenylylen-alpha-bromobenzylidene)s (7a and 7b) with mercury afforded the corresponding radicals, the ESR spectra of which were recorded. From the methyl substituted polymer 7b poly (2,2'5,5-tetramethyl-4,4'-bi-phenylylen)phenylmethylidyne was formed, whereas the unsubstituted product 7a was transformed into a para-quinoide polymer with radical properties.

Braun, D.↗
NASA NTRS1984

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

The Monte Carlo particle trajectory model for the saptial distribution of cometary radicals was modified to include the heliocentric distance dependence of the parent molecule velocity, and the heliocentric velocity dependence for CN fluorescence and radiation pressure. Available data on the observed spatial distributions of cometary radicals were studied and a preliminary comparison of newly published data from previous studies is discussed.

Combi, M. R.↗
NASA NTRS1985

Cometary atmospheres: Modeling the spatial distribution of observed neutral radicals

An algorithm for the random walk problem of multiple elastic collisions between newly formed non-thermal neutral cometary radicals and the outflowing cometary molecules was incorporated into the Monte Carlo particle-trajectory model. Preliminary model analysis has shown that the effects of collision on the observed spatial distribution of cometary radicals becomes important for the larger bright comets, especially at smaller values of the helicocentric distance. The model and early results are discussed herein.

Combi, M. R.↗
NASA NTRS1985

Ideal gas thermodynamic properties for the phenyl, phenoxy, and o-biphenyl radicals

Ideal gas thermodynamic properties of the phenyl and o-biphenyl radicals, their deuterated analogs and the phenoxy radical were calculated to 5000 K using estimated vibrational frequencies and structures. The ideal gas thermodynamic properties of benzene, biphenyl, their deuterated analogs and phenyl were also calculated.

Burcat, A.↗