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Relative gas-phase basicities of some aliphatic amines have been determined by ion cyclotron resonance spectroscopy. It is found that increasing alkyl substitution increases basicity if similar substituents are compared, that increases in alkyl group size also increase basicity, and that increasing degree of substitution lowers the N-H bond dissociation energy in ammonium ions. Possible origins of these defects are discussed.
In the past year, it was shown that in the 193 nm photolysis of C2H, the C2 radical is produced in a variety of electronic, vibrational, and rotational states. The relative population of the vibrational and rotational states of C2(A 1 Pi u), C2(B 1 Sigma g +), and C2(A 3 Pi u) were determined in a static gas cell and in a pulsed molecular beam. It seems as though the original angular momentum of the C2H molecule appears as part of the angular momentum of the C2 radical. A attempt is being made to discover the mathematical relationship that governs this mapping. New information about the bond dissociation energy of the C2 radical was produces. C2(b 3 Sigma g -) and C2( 1 Delta g) were detected in the photolysis of C2H via time resolved infrared emission spectroscopy. In the former case, vibrational excitation up to v'' = 4 is observed. All of the results suggest that the C2 models in comets need to consider the presence of vibrationally excited C2 radicals in comets. The laser induced fluorescence spectra of the C3 was observed as a product of the 193 nm photolysis of allene and propyne. The populations of the rotational levels are identical in both cases. This result has led us to conclude that an isomerization reaction occurs in the photolysis of propyne which leads to the same C3H2 intermediate that is formed in the photolysis of C3H4. Since the former molecule is one of the most abundant in the interstellar medium it is also likely that its precursor is also present in comets. This would explain why C3 is observed in comets.
Self-consistent field calculations are presented for HeCN(+) using several basis sets; calculations for HeH(+) with the same basis sets are given for comparison. These predict that HeCN(+) is stable with a He-CN(+) dissociation energy between 1.5 and 2.0 eV. The binding is found to be mainly electrostatic in nature. Rotation and hyperfine spectral constants are predicted. Similar calculations indicate that the isocyanide HeCN(+) is not stable. Preliminary calculations on NeCN(+) indicate that it is as stable as HeCN(+). The possibility of observing noble gas molecular ions in laboratory experiments and in interstellar space is discussed.
Thioperoxy (XSO or XOS) radicals exist in a variety of chemical environments, and they have as a consequence drawn some interest. HSO, an important species in the chemistry of the troposphere, has been examined both experimentally. The halogenated (X = F, Cl or Br) peroxy species and isovalent thioperoxy species have been studied less, but they too are potentially interesting because oxidized sulfur species and halogen sources are present in the atmosphere. Learning the fate of XSO and XOS radicals is important to understanding the atmospheric oxidation chemistry of sulfur compounds. Of these, FSO and ClSO are particularly interesting because they have been directly detected spectroscopically. Recent studies in our laboratory on the photochemistry of thionyl halides (X2SO; where X = F or Cl) have suggested new ways to generate XSO species. The laser-induced photodissociation of thionyl fluoride, F2SO, at 193 nm and thionyl chloride, ClSO, at 248 nm is characterized by a radical mechanism, X2SO -> XSO + X. The structure of FSO has been characterized experimentally by Endo et cd. employing microwave spectroscopy. Using the unrestricted Hartree-Fock (UHF) self-consistent field (SCF) method, Sakai and Morokuma computed the electronic structure of the ground (sup 2)A" and the first excited (sup 2)A' states of FSO. Electron correlation was not taken into account in their study. In a laser photodissociation experiment, Huber et al. identified ClSO mass spectromctrically. ClSO has also been detected in low temperature matrices by EPR and in the gas phase by far IR laser magnetic resonance. Although the structure of FSO is known in detail, the only study, experimental or theoretical, of CISO has been an ab initio HFSCF study by Hinchliffe. Electron correlation corrections were also excluded from this study. In order to better understand the isomerization and dissociation dynamics of the radical species, we have performed ab initio correlated studies of the potential energy surfaces (PES) of ClSO and its isomer ClOS at the QCISD(T)/6-31 G* level of theory. For FSO and FOS, more extensive QCISD/6-31 1G(2df) calculations have been possible, and the results are summarized here.
Hydroxyl tagging velocimetry (HTV) is a molecular tagging velocimetry (MTV) technique that relies on the photo- dissociation of water vapor into OH radicals and their subsequent tracking using laser-induced fluorescence. At ambient temperature in air, the OH species lifetime is about 50 micro-s. The feasibility of using HTV for probing low- speed flows (a few m/s) is investigated by using an inert, heated gas as a means to increase the OH species lifetime. Unlike particle-based techniques, MTV does not suffer from tracer settling, which is particularly problematic at low speeds. Furthermore, the flow needs to be seeded with only a small mole fraction of water vapor, making it safer for both the user and facilities than other MTV techniques based on corrosive or toxic chemical tracers. HTV is demonstrated on a steam-seeded nitrogen jet at approximately 75 C in the laminar (Umean=3.31 m/s, Re=1,540), transitional (Umean=4.48 m/s, Re=2,039), and turbulent (Umean=6.91 m/s, Re=3,016) regimes at atmospheric pressure. The measured velocity profiles are compared with particle image velocimetry (PIV) measurements performed simultaneously with a second imager. Seeding for the PIV is achieved by introducing micron-sized water droplets into the flow with the steam; the same laser sheet is used for PIV and HTV to guarantee spatial and temporal overlap of the data. Optimizing each of these methods, however, requires conflicting operating conditions: higher temperatures benefit the HTV signals but reduce the available seed density for the PIV through evaporation. Nevertheless, data are found to agree within 10% for the instantaneous velocity profiles and within 5% for the mean profiles and demonstrate the feasibility of HTV for low-speed flows at moderate to high temperatures.
A rocket-borne payload launched into an aurora and a simultaneous overpass of the Atmosphere Explorer C satellite yielded measurements of auroral optical emission rates, thermal ion and electron densities, and low-energy electron fluxes. Model calculations of the thermospheric manifestation of the aurora were performed through use of rocket-determined auroral ionization rates and satellite-determined neutral gas densities. Measured oxygen densities provided a means of assessing the quenching rate of an excited state of N2. Energy transfer from this excited state appears to be the major source of 5577-A emission. Optical emission at 6300 A cannot be explained either by electron impact on atomic oxygen or by dissociative recombination of O2(+).
The device considered utilizes an unsteady expansion process for the purpose of total-enthalpy multiplication. Analyses were conducted for both perfect and real air in equilibrium, assuming idealized diaphragm bursts, centered expansion waves, and continuum flow. Results of the study showed the expansion tube capable of outperforming the conventional shock tunnel by a factor of approximately 2 in velocity for the same test-section ambient density and pressure. The degree of dissociation is low at all phases of the thermodynamic cycle in the expansion tube; thus the test-section air has a good possibility of being in equilibrium. Maximum pressures involved in the cycle for duplicating a typical reentry from a lunar mission are low enough for existing pressure-vessel techniques. Both the known and anticipated advantages and disadvantages of this new concept are also discussed.
The flow about a body traveling at hypersonic speed is energetic enough to cause the atmospheric gases to chemically react and reach states in thermal nonequilibrium. The prediction of hypersonic flowfields requires a numerical method capable of solving the conservation equations of fluid flow, the chemical rate equations for specie formation and dissociation, and the transfer of energy relations between translational and vibrational temperature states. Because the number of equations to be solved is large, the numerical method should also be as efficient as possible. The proposed paper presents a fully implicit method that fully couples the solution of the fluid flow equations with the gas physics and chemistry relations. The method flux splits the inviscid flow terms, central differences of the viscous terms, preserves element conservation in the strong chemistry source terms, and solves the resulting block matrix equation by Gauss Seidel line relaxation.
Oxidation catalysts which operate at ambient temperature were developed for the recombination of carbon monoxide (CO) and oxygen (O2) dissociation products which are formed during carbon dioxide (CO2) laser operation. Recombination of these products to regenerate CO2 allows continuous operation of CO2 lasers in a closed cycle mode. Development of these catalyst materials provides enabling technology for the operation of such lasers from space platforms or in ground based facilities without constant gas consumption required for continuous open cycle operation. Such catalysts also have other applications in various areas outside the laser community for removal of CO from other closed environments such as indoor air and as an ambient temperature catalytic converter for control of auto emissions.
The Noble Metal Reducible Oxide (NMRO) catalysts for the low temperature oxidation of carbon monoxide were developed by NASA for the reoxidation of carbon monoxide which forms by the dissociation of carbon dioxide during the operation of sealed carbon dioxide lasers. The NMRO catalyst, which consists of a noble metal in conjunction with a reducible metal oxide, was evaluated under conditions that will be encountered in a CO2 laser operation, namely temperatures in the range 298 to 373 K and no significant reaction gas components other than CO, CO2 and O2. The NMRO catalysts may have significant potential for spin-off applications such as the prevention of carbon monoxide build-up in closed spaces as in space vehicle cabins or submarines, and the elimination of the cold start-up problem of automobile exhaust catalysts. The most significant difference in the conditions of these possible future applications is the high moisture content of the gases to be processed. Lack of understanding of the effects of water vapor and high temperature on catalyst activity and operation for extended periods are currently the main stumbling blocks for the transfer of this NASA technology to be used for commercial purposes. In the original proposal the following objectives were stated: To obtain experimental data on the adsorption, desorption and reaction characteristics of CO and CO2 the catalysts under high moisture conditions; to collect evidence on the presence of carbonate and hydroxyl surface species and their involvement in the CO oxidation mechanism; and to model the reaction system using a Monte-Carlo simulation to gain insight on the various steps involved. After the work has commenced the NASA technical monitor Mr. David Scheyer informed us that there was increased interest in the possible use of the NMRO catalysts as automobile exhaust catalysts and therefore NASA wanted to know whether the catalysts can operate at high temperatures as well as with high moisture gases. At that meeting it was decided that investigation of the high temperature performance of the NMRO catalysts should be given priority and replace the Monte-Carlo simulation objective. As a result, the modified objectives of the investigation were taken as the investigation of the high-temperature activity of the NMRO catalysts, and the effect of water vapor on the performance of these catalysts.
Reaction-rate theory and experiment are given a critical review from the engineers' point of view. Rates of heavy-particle, collision-induced reaction in gas phase are formulated in terms of the cross sections and activation energies for reaction. The effect of cross section function shape and of excited state contributions to reaction both cause the slope of Arrhenius plots to differ from the true activation energy, except at low temperature. The master equations for chemically reacting gases are introduced, and dissociation and ionization reactions are shown to proceed primarily from excited states about kT from the dissociation or ionization limit. Collision-induced vibration, vibration-rotation, and pure rotation transitions are treated, including three-dimensional effects and conservation of energy, which have usually been ignored. The quantum theory of transitions at potential surface crossing is derived, and results are found to be in fair agreement with experiment in spite of some questionable approximations involved.
In this contribution, we review our efforts toward understanding the typical mass-scale of primordial stars. Our direct numerical simulations show that, in both of Population III.1 and III.2 cases, strong UV stellar radiative feedback terminatesmass accretion onto a protostar.AnHII region formed around the protostar very dynamically expands throughout the gas accreting envelope, which cuts off the gas supply to a circumstellar disk. The disk is exposed to the stellar UV radiation and loses its mass by photoevaporation. The derived final masses are 43 Stellar Mass and 17 Stellar Mass in our fiducial Population III.1 and III.2 cases. Much more massive stars should form in other exceptional conditions. In atomic-cooling halos where H2 molecules are dissociated, for instance, a protostar grows via very rapid mass accretion with the rates M* approx. 0.1 - 1 Stellar Mass/yr. Our newstellar evolution calculations show that the protostar significantly inflates and never contracts to reach the ZAMS stage in this case. Such the "supergiant protostars" have very low UV luminosity, which results in weak radiative feedback against the accretion flow. In the early universe, supermassive stars formed through this process might provide massive seeds of supermassive black holes.
Photodissociation channels and the final product yields from the 193 nm photolysis of propene-h6 (CH2=CHCH3) and propene-d6 (CD2=CDCD3) have been investigated, employing gas chromatography, mass spectroscopy, and flame ionization (GC/MS/FID) detection methods. The yields of methane as well as butadiene relative to ethane show considerable variations when propene-h6 or propene-d6 are photolyzed. This suggests significant variances in the relative importance of primary photolytic processes and/or secondary radical reactions, occurring subsequent to the photolysis. Theoretical calculations suggest the potential occurrence of an intramolecular dissociation through a mechanism involving vinylidene formation, accompanied by an ethylenic H-migration through the pi-orbitals. This process affects the final yields of methane-h4 versus methane-d4 with respect to other products. The product yields from previous studies of the 193 nm photolysis of methyl vinyl ketone-h6 and -d6 (CH2=CHCOCH3, CD2=CDCOCD3), alternative precursors for generating methyl and vinyl radicals, are compared with the current results for propene.
The operation of a nuclear pumped laser, operating at a wavelength of 1.79 micron m on the 3d(1/2-4p(3/2) transition in argon with helium-3 as the majority gas is discussed. The energy pathways in He-Ar gas were investigated by observing the effects of varying partial pressures on the emissions of levels lying above the 4p level in argon during a pulsed afterglow. An attempt is made to determine the population mechanisms of the 3d level in pure argon by observing emission from the same transition in a high pressure plasma excited by a high energy electron beam. Both collisional radiative and dissociative recombination are discussed.
The possibility of using an IBr laser as a solar-energy converter is examined theoretically, and reasons for its choice are given. Broadband absorption results in dissociation with the formation of excited metastable Br atoms, some of which then lase to the ground state Br. The ground state is depopulated by three-body recombination and, more importantly, by exchange reactions which more than compensate for the high quenching in heteronuclear halogen systems. Kinetic modeling indicates lasing is possible in the pulsed mode and possibly in the steady state with a cooled gas flow system. Temperature effects are discussed. The efficiency of the laser approaches 1.2 percent at optical thicknesses large enough for complete absorption of the photons.
Tunable diode laser absorption spectroscopy has been employed to measure the amount of N2O produced from laser flash photolysis of O3/N2/O2 mixtures at 266 and 532 nm. In the 532 nm photolysis experiments very little N2O is observed, thus allowing an upper limit yield of 7 x 10(exp -8) to be established for the process O3 + N2 yield N2O + O2, where O3 is nascent O3 that is newly formed via O(3P(sub J)) + O2 recombination (with vibrational excitation near the dissociation energy of O3). The measured upper limit yield is a factor of approx. 600 smaller than a previous literature value and is approximately a factor of 10 below the threshold for atmospheric importance. In the 266 nm photolysis experiments, significant N2O production is observed and the N2O quantum yield is found to increase linearly with pressure over the range 100 - 900 Torr in air bath gas. The source of N2O in the 266 nm photolysis experiments is believed to be the addition reaction O(1D(sub 2)) + N2 + M yields (k(sub sigma)) N2O + M, although reaction of (very short-lived) electronically excited O3 with N2 cannot be ruled out by the available data. Assuming that all observed N2O comes from the O(1D(sub 2)) + N2 + M reaction, the following expression describes the temperature dependence of k(sub sigma) (in its third-order low-pressure limit) that is consistent with the N2O yield data: k(sub sigma) = (2.8 +/- 0.1) x 10(exp -36)(T/300)(sup -(0-88+0.36)) cm(sup 6) molecule(sup -2)/s, where the uncertainties are 2(sigma) and represent precision only. The accuracy of the reported rate coefficients at the 95% confidence level is estimated to be 30 - 40% depending on the temperature. Model calculations suggest that gas phase processes initiated by ozone absorption of a UV photon represent about 1.4% of the currently estimated global source strength of atmospheric N2O. However, these processes could account for a significant fraction of the oxygen mass-independent enrichment observed in atmospheric N2O, and they appear to be the first suggested photochemical mechanism that is capable of explaining the altitude dependence of the observed mass -independent isotopic signature.
Enhanced scattering and fluorescence processes in the visible and UV were investigated which will enable improved remote measurements of gas properties. The theoretical relationship between scattering and fluorescence from an isolated molecule in the approach to resonance is examined through analysis of the time dependence of re-emitted light following excitation of pulsed incident light. Quantitative estimates are developed for the relative and absolute intensities of fluorescence and resonance scattering. New results are obtained for depolarization of scattering excited by light at wavelengths within a dissociative continuum. The experimental work was performed in two separate facilities. One of these utilizes argon and krypton lasers, single moded by a tilted etalon, and a 3/4 meter double monochromator. This facility was used to determine properties of the re-emission from NO2, I2 and O3 excited by visible light. The second facility involves a narrow-line dye laser, and a 3/4 meter single monochromator. The dye laser produces pulsed light with 5 nsec pulse duration and 0.005 nm spectral width.
We present results from a KAO survey of fine-structure lines observed in 23 infrared-luminous galaxies. One or more of the following lines was observed and/or detected in each galaxy: (S III) 19, 33 microns, (Ne V) 24 microns, (O IV) 26 microns, (Fe II) 26 microns, (Si II) 35 microns, (O III) 52, 88 microns, (0 I) 63, 146 microns, (N III) 57 micro ns, (N II) 122, 205 microns, (C II) 158 microns. The galaxies span a wide range of morphologies (irregular to grand design), have varying metallicities, and include mergers, AGN's, and starburst systems. The observations were made beginning in 1988 using the facility Cryogenic Grating Spectrometer onboard the KAO at a typical resolution of approximately 60-140 km/s and with a 30-44 deg beam. We interpret the (C II) and (O I) fluxes, along with previous measurements of the IR continuum fluxes, in the context of photo dissociation region (PDR) models (Tielens & Hollenbach 1985; Wolfire et al. 1990). With these models, we obtain estimates of the typical interstellar UV fields incident on the line emitting regions (102-104 times the local interstellar radiation field) and the total masses (10(exp 7)-10(exp 8) Solar Mass), densities (10(exp 3)-10(exp 4)/cu cm), and temperatures (100-250 K) of the warm atomic gas. The (O III) (52/88) and (S III) (33/19) line flux ratios constrain the range of electron densities and pressures found within the ionized regions. The (O III) and (S III) lines also provide estimates of the effective temperature of the ionizing stars and elemental abundances within the ionized regions of these galactic nuclei. Our measurements imply typical gas pressures of nT approximately 5 x 10(exp 6)/cu cm K and typical upper mass cutoffs of 25-35 Solar Mass. The low-metallicity systems show high (C II)/CO and (O I)/CO flux ratios, 3-5 times the Milky Way value, indicating that they contain a larger fraction of photodissociated gas relative to the molecular material.