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Cross sections for the production of N2(+), N(+) + N2(2+) and N(2+) by electron impact on N2 have been measured for an energy range from threshold to 1000 eV. These cross sections have been fitted to an empirical formula for future use in modeling various plasmas. Considerable differences from some previous data have been found.
Recent work in the aerothermodynamics community has focused on the development of reduced-order models for thermo-chemical non-equilibrium which avoid the restrictive assumptions of multi-temperature models and the prohibitive cost associated with State-to-State (StS) models. In the present work, this is accomplished by lumping energy states together and assuming groups of states are roughly in equilibrium. As a result, the non-equilibrium behavior of a gas can be captured at a reduced computational cost from a full StS simulation. In this work, we present a hybrid grouping model for studying energy transfer and dissociation in a mixture of nitrogen molecules due to N2-N2 reactions. This is accomplished by making use of a grouping strategy informed by data from the N2-N StS kinetic data. However, due to the massive computational cost associated with constructing StS data for the N2-N2 system, the kinetic data for the hybrid grouping model are calculated using the quasi-classical trajectory (QCT) method by sampling states for trajectory within the groups. This general framework is called the Maximum-Entropy Quasi-Classical Trajectory (ME-QCT) method. The primary challenge associated with this method is that rates for reverse grouped reactions cannot be obtained through detailed balance at a group level, due to the variation of group internal temperatures. To construct the full model for N2-N2 grouped kinetics using the ME-QCT method, detailed balance is invoked at the microscopic level, allowing for the calculation of the full kinetic data from QCT. Results will be presented using the full ME-QCT model for the N2-N2 system in an isothermal and isochoric reactor simulation. In addition, simple CFD test cases for a one-dimensional standing shock and for a quasi-one-dimensional nozzle will be used for demonstration of the ME-QCT method. This method allows for the calculation of non-equilibrium behavior for the N2-N2 system without the prohibitive cost of a full StS simulation. Moreover, it enables the construction of a unified model for the dissociating and recombining non-equilibrium flows.
In this paper, we report measured Lorentz N2-broadening and N2-induced pressure-shift coefficients of CH3D in the v2 fundamental band using a multispectrum fitting technique. These measurements were made by analyzing 11 laboratory absorption spectra recorded at 0.0056 cm(exp -1) resolution using the McMath-Pierce Fourier transform spectrometer located at the National Solar Observatory on Kitt Peak, Arizona. The spectra were obtained using two absorption cells with path lengths of 10.2 and 25 cm. The total sample pressures ranged from 0.98 to 402.25 Torr with CH3D volume mixing ratios of 0.01 in nitrogen. We have been able to determine the N2 pressure- broadening coefficients of 368 v2 transitions with quantum numbers as high as J"= 20 and K = 16, where K" = K' equivalent to K (for a parallel band). The measured N2-broadening coefficients range from 0.0248 to 0.0742 cm(exp -1) atm(exp -1) at 296 K. All the measured pressure-shifts are negative. The reported N2-induced pressure-shift coefficients vary from about 0.0003 to 0.0094 cm(exp -1) atm(exp -1). We have examined the dependence of the measured broadening and shift parameters on the J", and K quantum numbers and also developed empirical expressions to describe the broadening coefficients in terms of m (m = -J", J", and J" + 1 in the (sup Q)P-, (sup Q)Q-, and (sup Q)R-branch, respectively) and K. On average, the empirical expressions reproduce the measured broadening coefficients to within 4.7%. The N2-broadening and pressureshift coefficients were calculated on the basis of a semiclassical model of interacting linear molecules performed by considering in addition to the electrostatic contributions the atom atom Lennard-Jones potential. The theoretical results of the broadening coefficients are in good overall agreement with the experimental data (8.7%). The N2-pressure shifts whose vibrational contribution is derived from parameters fitted in the (sup Q)Q-branch of self-induced shifts of CH3D, are also in reasonable agreement with the scattered experimental data (20% in most cases).
Characteristics of Meinel systems excited by electrons and measurement of transition probabilities, excitation cross sections, and afterglow effects
Absolute total negative charge production cross sections for N2 + CO, CO + N2, CO + CO, N2 + NO, N2 + CH4, and N2 + CO2 collisions are reported, and a simple model of collisions is discussed. The cross sections were measured to within about 1 eV of their thresholds. Specific reaction channels were investigated by referring to mass spectrometric identification of the product ions scattered in the forward direction, and these product ion identifications were used to explain characteristic structures in the total charge production cross sections in the near-threshold regions. The extent of the importance of dissociative ionization and 'simple' ionization in the studied collisions at low energy is considered, and charge transfer cross sections for (CO)+ + CO, CO(+) + CH4, and N2(+) + CH4 are presented.
Study of the mechanism of formation of the N3(+) ion from the bimolecular reaction of excited N2(+) ions in gaseous N2. Using ion cyclotron resonance spectroscopy, an attempt is made to inquire more deeply than hitherto into the origin of the N3(+) ions and to determine the rate constant for their formation and the limits on the lifetime of the reactant excited N2(+) ions.
The dc glow discharges in different gas mixtures of Ar + N2, Ar + NH3 or Ar + N2 + H2 result in the surface nitriding of Ti metal and its alloy (Ti6Al4V). Various gas mixtures were used in order to establish the main active species governing the nitriding process, i.e., N, N2, NH, or NH2 as excited or ionized particles. The dc discharge was sampled and analyzed by quadruple mass spectrometry (QPMS) and optical emission spectroscopy (OES), and the nitrided samples were analyzed by scanning electron microscopy (SEM) with an EDAX attachment, microhardness, and Fourier transform infrared reflectance spectrometry (FTIR). It was found that the excited and ionized nitrogen and hydrogen atoms are the main species responsible for the nitriding process in a dc glow discharge.
The objectives of this program are to further the understanding of the upper atmospheres of Titan, Triton, and the Earth in terms of the observed emissions of the 13-14 eV states of N2. These states are generated at quite high rates, yet very little emission is observed from them. The reasons are complex, involving resonance trapping and predissociation, and it is desired to quantify the effects of predissociation, particularly on the c(sub 4)' 1 Sigma(sub u),(sup +) state of N2. Earlier experiments had indicated that predissociation of the c(sub 4)' state was of little importance, yet over the last two years a growing body of evidence has shown that for levels above v = 2, predissociation is in fact a major process. It is the v = 0 level for which production by electron bombardment and photoexcitation is highest, and so it has been most important to evaluate the effects of predissociation on this particular level. The goal has been to target c(sub 4)' (v = 0) for a thorough analysis, in which both the extent of predissociation as a function of rotational level and the atomic product branching ratio, where the only possible products are N(4S) + N(4S) and N(2D) + N(4S), are determined. For the first year of funding, the intention was to demonstrate two-photon excitation of the intermediate N2(a(sup 1) Pi(sub g)) state, so that the gap to the 13 eV energy region could be bridged, and then use a second laser to reach the c(sub 4)' state itself.
Rotational inelastic transitions of N2 have been studied in the coupled state (CS, also called centrifugal sudden) and infinite-order-sudden (IOS) approximations, using the N2-N2 rigid-rotor potential of van der Avoird et al. For benchmarking purposes, close coupling (CC) calculations have also been carried out over a limited energy range and for even j - even j collisions only. Both the CC and CS cross sections have been obtained with and without exchange symmetry, whereas exchange is neglected in the IOS calculations. The CS results track the CC cross sections rather well. At total energies between 113 to 219 cm(exp -1) the average deviation is 14%. The deviation decrease with increasing energy, indicating that the CS approximation can be used as a substitute at higher energies when the CC calculations become impractical. Comparison between the CS and IOS cross sections at the high energy end of the CS calculation, 500 - 680 cm(exp-1), shows significant differences between the two. In addition, the IOS results exhibits sensitivity to the amount of inelasticity and the results for large DELTA J transitions are subjected to bigger errors. At total energy 113 cm(exp -1) and above, the average deviation between state-to-state cross sections calculated with even and odd exchange symmetries is 1.5%.
Use of the relative emission rates of the auroral N2 positive and N2(+) band systems to limit the permissible range of differential electron fluxes in auroras, due to remarkable differences in electron excitation functions for the two kinds of systems. Use of recently measured electron cross sections and many observational data from ground based and rocket studies shows that the results are consistent with spectra equivalent to a power law E to the minus 1.4 power for primaries and secondaries combined. The unified primary spectra of Rees (1969) and secondary spectra of Rees et al. (1969) fail seriously to predict the optical ratios. It is shown that Rees' primary spectrum is deficient in slow primaries, owing to the use of defective Monte Carlo results of Maeda (1965). Doubt is thereby cast on the validity of experimental results for the differential spectrum below 50 eV reported by Feldman et al. (1971) because of the rapid decrease in flux with energy shown by those measurements.
A computational method is proposed to obtain rotational transition probabilities in collisions between two diatomic molecules. The potential method of Rabitz and an exponential approximation are used to solve the semiclassical coupled equations without invoking any perturbational technique. The collision trajectory is determined in the classical modified-wave-number approximation. The method can treat systems involving strong interactions and provide probabilities for transitions even with a multiquantum jump. A simultaneous transition in the rotational states of both molecules, i.e., the rotational-rotational energy transfer, is taken into account. An application to the system N2 + N2 is presented.
Rate constants for the reaction O + NO + N2 yields NO2 + N2 from 217 to 500 K were obtained by a method combining the flash photolysis of NO with the time resolved detection of O by means of resonance fluorescence. The rate constants were found to obey the Arrhenius equation k = (15.5 plus or minus 2.0) x 10 to the -33rd exp((1160 plus or minus 70)/1.987 T) cm to the 6th/squared molecule/s, while the temperature dependence of k is described by k = 3.80 x 10 to the -27th/T to the 1.82 cm to the 6th/squared molecule/s.
The Atmosphere Explorer (AE) data are reexamined in the light of new laboratory measurements of the N2(+) recombination rate coefficient alpha. The new measurements support earlier measurements which yielded values of alpha significantly lower than the AE values. It is found that the values for alpha determined from the satellite data can be reconciled with the laboratory measurements, if the charge exchange rate coefficient for O(+)(2D) with N2 is less than one-quarter of that derived in the laboratory by Rutherford and Vroom (1971).
Theoretical spectroscopic constants are reported for the A prime 5Sigma(+)g and C double prime 5Pi u states of N2 based on CASSCF/MRCI calculations using large ANO Gaussian basis sets. The calculated A prime Sigma(+)g potential differs qualitatively from previous calculations in that the inner well is significantly deeper (De = 3450/cm). This deeper well provides considerable support for the suggestion of Berkowitz et al. (1956) that A prime 5Sigma(+)g is the primary precursor state involved in the yellow Lewis-Rayleigh afterglow of N2.
Techniques were developed for recovering two-dimensional distributions of auroral volume emission rates from rocket photometer measurements made in a tomographic spin scan mode. These tomographic inversion procedures are based upon an algebraic reconstruction technique (ART) and utilize two different iterative relaxation techniques for solving the problems associated with noise in the observational data. One of the inversion algorithms is based upon a least squares method and the other on a maximum probability approach. The performance of the inversion algorithms, and the limitations of the rocket tomography technique, were critically assessed using various factors such as (1) statistical and non-statistical noise in the observational data, (2) rocket penetration of the auroral form, (3) background sources of emission, (4) smearing due to the photometer field of view, and (5) temporal variations in the auroral form. These tests show that the inversion procedures may be successfully applied to rocket observations made in medium intensity aurora with standard rocket photometer instruments. The inversion procedures have been used to recover two-dimensional distributions of auroral emission rates and ionization rates from an existing set of N2+3914A rocket photometer measurements which were made in a tomographic spin scan mode during the ARIES auroral campaign. The two-dimensional distributions of the 3914A volume emission rates recoverd from the inversion of the rocket data compare very well with the distributions that were inferred from ground-based measurements using triangulation-tomography techniques and the N2 ionization rates derived from the rocket tomography results are in very good agreement with the in situ particle measurements that were made during the flight. Three pre-prints describing the tomographic inversion techniques and the tomographic analysis of the ARIES rocket data are included as appendices.
Photon emission spectra resulting from the impact of N2, N2(+), and electron beams on magnesium fluoride in an ultrahigh vacuum environment were measured and compared for beam energies in the range 200-2000 eV. Unexpectedly, only the ion- and electron-induced spectra exhibited broad fluorescence. The observed data suggest that the broad fluorescence arising from low-energy ion bombardment is due primarily to the transfer of electronic energy to the surface by resonance or Auger neutralization. Since molecular nitrogen is a major constituent of the atmosphere at orbital altitudes, these measurements bear directly on radiation-induced glow and erosion processes on surfaces of spacecraft in low-earth orbit.
This work presents a general framework for model reduction of non-equilibrium energy transfer and dissociation processes. The multi-group maximum-entropy method is coupled with the quasi-classical trajectory method to directly construct a reduced order model for chemical non-equilibrium. Kinetic data is calculated by applying detailed balance at a microscopic level, overcoming the limitation of calculating recombination kinetic data. This approach enables the construction of a reduced order model for kinetics which bypasses the need to compute state-to-state kinetic data. This physics based reduced order model ensures that an equilibrium distribution is reached given infinite time, while allowing for non-equilibrium distributions during the relaxation and dissociation processes. A proof-of-concept test case demonstrates the applicability of this model by comparison with state-to-state kinetic data for the N2(Chi (sup 1) Sigma ((sub g), (sup plus sign)) minus N ((exp 4) S (sub u)) system with excellent agreement.
In this work, Complex Robert-Bonamy calculations of half-widths and line shifts were done for N2-broadening of water for 1639 transitions in the rotational band using two models for the trajectories. The first is a model correct to second order in time, the Robert-Bonamy parabolic approximation. The second is the solution of Hamilton's equations. Both models use the isotropic part of the atom-atom potential to determine the trajectories. The present calculations used an intermolecular potential expanded to 20th order to assure the convergence of the half-widths and line shifts. The aim of the study is to assess if the difference in the half-widths and line shifts determined from the two trajectory models is greater than the accuracy requirements of the spectroscopic and remote sensing communities. The results of the calculations are compared with measurements of the half-widths and line shifts. It is shown that the effects of the trajectory model greatly exceed the needs of current remote sensing measurements and that line shape parameters calculated using trajectories determined by solving Hamilton's equations agree better with measurement.