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At least 271 records · Page 15

Self-, N2- and Ar-broadening and line mixing in HCN and C2H2

Self-, N2- and Ar-broadening coefficients were measured for the stretch-bend infrared combination bands nu-1 + nu-1/2 (4004/cm) of HCN and nu-1 + nu-1/5 (4091/cm) of C2H2, using a tunable difference-frequency laser. At atmospheric pressures, the Q branches of these bands exhibit significant rotational narrowing or line mixing. The broadening coefficients are fit with empirical rotationally inelastic collision rate laws, which are then used to model the line mixing in the overlapped Q-branch profiles. Simple energy gap fitting laws appear to be suitable for the shorter-range intermolecular quadrupole-quadrupole and induction forces, whereas an energy-corrected-sudden scaling law works better for the longer-range dipole-dipole and dipole-quadrupole collision partners. In all cases, the line-coupling coefficients are substantially reduced from the rotationally inelastic rates fit to the broadening coefficients, indicating that 35-70 percent of the broadening may be due to other collisional mechanisms such as cross-relaxation to the degenerate H state vibrational level.

Pine, A. S.↗

N2 Lyman-Birge-Hopfield dayglow from ATLAS 1

Spectral measurements of the far ultraviolet dayglow were made from the ATLAS 1 shuttle mission using an intensified charge coupled device (CCD) imaging spectrometer array. The instrument imaged relatively large (177 A) segments of the spectrum simultaneously and had the capability to image altitude in the second dimension of the two-dimensional focal plane detector when the entrance slit of the instrument was oriented perpendicular to the limb of the Earth. The far ultraviolet (FUV) channel of the instrument used a CsTe photocathode rather than the more conventionally used and more solar blind CsI photocathode material. As a result, the spectra were also measured with good sensitivity at FUV wavelengths longer than 1500 A. In this paper, data are selected of specific interest to a study of the N2 Lyman-Birge-Hopfield system using two shuttle attitudes: In the first the field of view was held at a fixed tangent ray height of approximately 140 km while scanning in wavelength, providing repeated FUV spectra over a range of latitudes and allowing comparison with our thermospheric airglow model. In the second observing sequence the line of sight of the instrument was scanned down through the atmosphere but covered about 75% of the full wavelength range. This sequence allows comparison of height dependence,including O2 absorption effects, with the thermospheric model. In all cases, relatively good agreement is obtained with the model (run strictly in a predictive mode) in comparisions in which the line of sight must be intergrated along a path that spans a considerable range of conditions (height, local time, latitude, solar zenith angle). In the case of the data sets examined in this study the vibrational population distributions show mixed results. In one case the distribution agrees well with a theoretical model based on direct electron impact excitation without a significant cascade contribution. A second case indicated a lower population in nu' = 3 and a higher population in nu' = 6 than would be expected from direct impact excitation alone. This supports previous indications that conditions resulting in the cascade mechanism may not always be operative.

Torr, Marsha R.↗

Pressure broadening of vibrational Raman lines in N2 at temperatures below 300 K

Using quasi-cw stimulated Raman gain spectroscopy, the pressure broadening coefficients for the N2 vibrational Q-branch transitions have been measured over the temperature range 113-297 K for the rotational components J = 4, 6, 8, 10, and 12. The experimental results are fit to a simple power law to give an empirical formula for the temperature dependence of the pressure broadening over the 100-300 K range. These results are also compared to previously published scaling laws that are based on collision induced rotational transition rates.

Herring, G. C.↗

Primary results from the Berkeley EUV airglow rocket spectrometer: O I and N2 FUV/EUV dayglow in the thermosphere and lower exosphere

The Berkeley extreme-ultraviolet airglow rocket spectrometer (BEARS) made spectroscopic measurements of far and extreme UV, atomic oxygen emissions from a Black Brandt XII (12.041 WT) sounding rocket launched from Wallops Island, Virginia, on September 30, 1988. BEARS' primary instrument, a near-normal Rowland mount spectrometer, measured several atomix oxygen and molecular nitrogen dayglow features at high spectral resolution (1.5 A): O I (989, 1027, 1304, and 1356 A); and N2 Lyman-Birge-Hopfield (4, 0) and (3, 0) bands at 1325 and 1354 A. The instrument collected over 800 s of data spanning altitudes of 150 - 963 km with look directions between 95 deg and 125 deg from zenith. We have analyzed the data using electrons and radiative transport models in a forward modeling approach. The model and data are generally in good agreement. However, there are some discrepancies, which are discussed in terms of remote sensing capabilities and improvements to the models.

Cotton, Daniel M.↗

Pressure broadening of ClO by N2 and O2 near 204 and 649 GHz and new frequency measurements between 632 and 725 GHz

The N2 and O2 pressure broadening of the ClO transitions near 204 and 649 GHz have been measured between 200 and 300 K. Oxygen broadening has been measured for the transitions near 278 GHz. The accuracy of the derived air broadening is comparable to that for the air broadening of stable species and is estimated to be within approximately 3% over the entire temperature range. These transitions are currently being used for satellite, balloon, and ground based monitoring of atmospheric ClO, respectively. Some new frequency measurements are reported in the 632 - 725 GHz range. These are in good agreement with previous measurements and predictions.

Oh, J. J.↗

O2 Herzberg State Reaction with N2: A Possible Source of Stratospheric N2O

The goal of this one-year investigation was to determine whether N2O is formed in atmospherically significant quantities by the reaction of vibrationally excited levels of the O2((A3 Sigma(sub u)(sup +)) state with nitrogen. O2(A3 Sigma(sub u)(sup +)) is made throughout the upper stratosphere in considerable amounts by solar photoabsorption, and only a very small reactive yield is necessary for this mechanism to be a major N2O source. By long-term 245-252 nm irradiation of O2/N2 mixtures on- and off-resonance with absorption lines in the O2(A3 Sigma(sub u)(sup +) - X3 Sigma(sub g)(sup -)) transition, followed by N2O analysis by frequency-modulated diode laser absorption spectroscopy, we determined an upper limit for the N2O yield of the candidate reaction. This limit, 3 x 10(exp -5), eliminates O2(A3 Sigma(sub u)(sup +)) + N2 as a significant channel for the generation of stratospheric N2O. In further measurements, we established that N2O is stable under our photolysis conditions, showing that the small amounts of ozone generated from the reaction of O2(A) and O2 do not indirectly lead to destruction of N2O.

Slanger, Tom G.↗

Collisional Removal of OH (X (sup 2)Pi, nu=7) by O2, N2, CO2, and N2O

Collisional removal rate constants for the OH (X 2PI, nu = 7) radical are measured for the colliders O2, CO2, and N2O, and an upper limit is established for N2. OH(nu = 4) molecules, generated in a microwave discharge flow cell by the reaction of hydrogen atoms with ozone, are excited to v = 7 by the output of a pulsed infrared laser via direct vibrational overtone excitation. The temporal evolution of the P = 7 population is probed as a function of the collider gas partial pressure by a time-delayed pulsed ultraviolet laser. Fluorescence from the B 21 + state is detected in the visible spectral region.

Knutsen, Karen↗

Charge Transfer Between Ground-State N(2+) and H2, N2, and CO at Electron-Volt Energies

The charge-transfer rate coefficients for reactions of N(2+)(2 S(sup 2)2p(sup 2)P(sup 0)) with H2, N2, and CO are measured using ion storage. A cylindrical rf ion trap was used to store N(2+) ions produced by laser ablation of a solid titanium nitride target. The rate coefficients were derived from the decay rate of the ion signal. The rate coefficients for the above three reactions are 3.38(0.35) x 10(exp -11)sq sm/s at T(sub equiv.)=2.9 x 10(exp 3) K, 2.10(0.18) x 10(exp -9)sq sm/s at T(sub equiv.) = 1.3 x 10(exp 4) K, and 3.37(0.29) x 10(exp -9)sq cm/s at T(sub equiv.) = 1.3 x 10(exp 4) K, respectively. No theoretical or other experimental values are available at this energy range.

Fang, Z.↗

Measurement of Momentum Transfer Coefficients for H2, N2, CO, and CO2 Incident Upon Spacecraft Surfaces

Measurements of momentum transfer coefficients were made for gas-surface interactions between the Space Shuttle reaction control jet plume gases and the solar panel array materials to be used on the International Space Station. Actual conditions were simulated using a supersonic nozzle source to produce beams of the gases with approximately the same average velocities as the gases have in the Shuttle plumes. Samples of the actual solar panel materials were mounted on a torsion balance that was used to measure the force exerted on the surfaces by the molecular beams. Measurements were made with H2, N2, CO, and CO2 incident upon the solar array material, Kapton, SiO2-coated Kapton, and Z93-coated Al. The measurements showed that molecules scatter from the surfaces more specularly as the angle of incidence increases and that the scattering behavior has a strong dependence upon both the incident gas and velocity. These results show that for some technical surfaces the simple assumption of diffuse scattering with complete thermal accommodation is entirely inadequate. It is clear that additional measurements are required to produce models that more accurately describe the gas-surface interactions encountered in rarefied flow regimes.

Cook, Steven R.↗

Measurements of momentum transfer coefficients for H2, N2, CO and CO2 incident upon spacecraft surfaces

Measurements of momentum transfer coefficients were made for gas-surface interactions between the Space Shuttle reaction control jet plume gases and the solar panel array materials to be used on the International Space Station. Actual conditions were simulated using a supersonic nozzle source to produce beams of the gases with approximately the same average velocities as the gases have in the Shuttle plumes. Samples of the actual solar panel materials were mounted on a torsion balance that was used to measure the force exerted on the surfaces by the molecular beams. Measurements were made with H2, N2, CO, and CO2 incident upon the solar array material, Kapton, SiO2-coated Kapton, and Z93-coated Al. The measurements showed that molecules scatter from the surfaces more specularly as the angle of incidence increases and that scattering behavior has a strong dependence upon both the incident gas and velocity. These results show that for some technical surfaces the simple assumption of diffuse scattering with complete thermal accommodation is entirely inadequate. It is clear that additional measurements are required to produce models that more accurately describe the gas-surface interactions encountered in rarefied flow regimes.

Cook, S. R.↗

Fast Nitrogen Atoms from Dissociative Excitation of N2 by Electron Impact

The Doppler profiles of one of the fine structure lines of the N I (1200 A) g (sup 4)S(sup 0)-(sup 4)P multiplet and of the N II (1085 A) g (sup 3)p(sup O)-(sup 3)D multiplet have been measured. Excitation of the multiplets is produced by electron impact dissociative excitation of N2. The experimental line profiles are evaluated by fast Fourier transform (FFT) techniques and analysis of the profiles yields the kinetic energy distribution of fragments. The full width at half maximum (FWHM) of N I (1200 A) increases from 27+/-6 mA at 30 eV to 37+/-4 mA at 100 eV as the emission cross section of the dissociative ionization excitation process becomes more important relative to the dissociative excitation process. The FWHM of the N II (1085 A) line is 36+/-4 mA at 100 eV. For each multiplet the kinetic energy distribution function of each of the two fragment N atoms (ions) is much broader than thermal with a mean energy above 1.0 eV. The dissociation process with the largest cross section is predissociation and predominantly produces N atoms with kinetic energy distributions having mean energies above 0.5 eV. Dissociative processes can lead to a substantial escape flux of N I atoms from the satellites, Titan and Triton of the outer planets.

Ajello, Joseph M.↗

The Density Matrix of H20 - N2 In the Coordinate Representation: A Monte Carlo Calculation of the Far-Wing Line Shape

The far-wing line shape theory within the binary collision and quasistatic framework has been developed using the coordinate representation. Within this formalism, the main computational task is the evaluation of multidimensional integrals whose variables are the orientational angles needed to specify the initial and final positions of the system during transition processes. Using standard methods, one is able to evaluate the 7-dimensional integrations required for linear molecular systems, or the 7-dimensional integrations for more complicated asymmetric-top (or symmetric-top) molecular systems whose interaction potential contains cyclic coordinates. In order to obviate this latter restriction on the form of the interaction potential, a Monte Carlo method is used to evaluate the 9-dimensional integrations required for systems consisting of one asymmetric-top (or symmetric-top) and one linear molecule, such as H20-N2. Combined with techniques developed previously to deal with sophisticated potential models, one is able to implement realistic potentials for these systems and derive accurate, converged results for the far-wing line shapes and the corresponding absorption coefficients. Conversely, comparison of the far-wing absorption with experimental data can serve as a sensitive diagnostic tool in order to obtain detailed information on the short-range anisotropic dependence of interaction potentials.

Ma, Q.↗

Finite-Element Z-Matrix Calculation of Electron-N2 Collisions

The finite element Z-matrix method has been applied in a multichannel study of e-N2 Collisions for electron energies from threshold to 30 eV. General agreement is obtained comparing with existing experimental and theoretical data. Some discrepancies are also found.

Huo, Winifred M.↗

The Effects of Flame Structure on Extinction of CH4-O2-N2 Diffusion Flames

The effects of flame structure on the extinction limits of CH4-O2-N2 counterflow diffusion flames were investigated experimentally and numerically by varying the stoichiometric mixture fraction Z(sub st), Z(sub st) was varied by varying free-stream concentrations, while the adiabatic flame temperature T(sub ad) was held fixed by maintaining a fixed amount of nitrogen at the flame. Z(sub st) was varied between 0.055 (methane-air flame) and 0.78 (diluted- methane-oxygen flame). The experimental results yielded an extinction strain rate K(sub ext) of 375/s for the methane-air flame, increasing monotonically to 1042/s for the diluted-methane-oxygen flame. Numerical results with a 58-step Cl mechanism yielded 494/s and 1488/s, respectively. The increase in K(sub ext) with Z(sub st) for a fixed T(sub ad) is explained by the shift in the O2 profile toward the region of maximum temperature and the subsequent increase in rates for chain-branching reactions. The flame temperature at extinction reached a minimum at Z(sub st) = 0.65, where it was 200 C lower than that of the methane-air flame. This significant increase in resistance to extinction is seen to correspond to the condition in which the OH and O production zones are centered on the location of maximum temperature.

Du, J.↗

The Theoretical Transition Probabilities Between the B(sup 3)Pi(sub g) and the A(sup 3)Sigma(Sup +, sub u), W(sup 3)Delta(sub u), B'(sup 3)Sigma(sup -, sub u) States of N2

The electronic transition moment functions between the B(sup 3)Pi(sub g) and the A(sup 3)Sigma(sup +, sub u), W(sup 3)Delta(sub u), B'(sup 3)Sigma(sup -, sub u) states of N2 are studied using the internally contracted multireference configuration interaction (ICMRCI) method based upon complete active space SCF (CASSCF) reference wave-functions. The dependence of the moments on both the one and n-particle basis sets has been investigated in detail. The calculated radiative lifetimes for the vibrational levels of B(sup 3)Pi(sub g) are in excellent agreement with the most recent measurement of Euler and Pipkin (1983)

Thuemmel, Helmar T.↗

UV photoabsorption cross sections of CO, N2, and SO2 for studies of the ISM and planetary atmospheres

We report high-resolution laboratory measurements of photoabsorption cross sections of CO, N2, and SO2 in the wavelength range 80 to 320 nm. The motivation is to provide the quantitative data that are needed to analyze observations of absorption by, and to model photochemical processes in, the interstellar medium and a number of planetary atmospheres. Because of the high resolution of the spectrometers used, we can minimize distortion of the spectrum that occurs when instrument widths are greater than the widths of spectral features being measured. In many cases, we can determine oscillator strengths of individual rotational lines - a unique feature of our work.

Smith, Peter L.↗

Reactive Resonances in N+N2 Exchange Reaction

Rich reactive resonances are found in a 3D quantum dynamics study of the N + N2 exchange reaction using a recently developed ab initio potential energy surface. This surface is characterized by a feature in the interaction region called Lake Eyring , that is, two symmetric transition states with a shallow minimum between them. An L2 analysis of the quasibound states associated with the shallow minimum confirms that the quasibound states associated with oscillations in all three degrees of freedom in Lake Eyring are responsible for the reactive resonances in the state-to-state reaction probabilities. The quasibound states, mostly the bending motions, give rise to strong reasonance peaks, whereas other motions contribute to the bumps and shoulders in the resonance structure. The initial state reaction probability further proves that the bending motions are the dominating factors of the reaction probability and have longer life times than the stretching motions. This is the first observation of reactive resonances from a "Lake Eyring" feature in a potential energy surface.

Wang, Dunyou↗