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The threshold for collisionless dissociation of SF6, SiF4, and CF2Cl2 by focused CO2 laser radiation has been measured. This threshold is a laser pulse energy effect and, within experimental error, is found to be the same for all three gases. Provided collisions cannot occur during the laser pulse, the degree of dissociation produced depends only on the energy in the pulse, which is consistent with simple adiabatic vibrational heating of the molecules by the laser.
Reactions of various positive ions with water vapor were studied by ion cyclotron resonance mass spectrometric techniques. Rate constants and product distributions were determined for reactions of the ions: Ar(+), Co(+), N2(+), and CO2(+), CH2(+), and CH4(+), CH2Cl(+), HCO(+), H2CO(+), H2COH(+), H2S(+) and HS(+). The results obtained in this work are compared with earlier reported data where available.
Differential, integral, momentum transfer, and partial cross sections have been calculated for elastic scattering and rotational excitation of C2H2 by 10-eV electrons. The effective potential includes static, exchange, and polarization interactions calculated by the INDOX/1s method and the semiclassical exchange approximation with adiabatic polarization at large electron-molecule distances. The scattering is treated by well converged rotational close coupling using the centrifugal dominant scheme to select the channels included and including up to 32 coupled channels for a given total angular momentum. The calculated integral cross sections for pure elastic scattering and rotation excitation are 54.5 and 41.4 a(0)squared, respectively. These are much larger than the values (34.4 and 18.6 a(0)squared) previously (Onda and Truhlar, 1979) calculated for the isoelectronic molecule N2, at this energy. This illustrates how the greater spatial extent of C2H2 greatly increases the cross sections for pure elastic and rotationally inelastic scattering.
The detection of the acetylene derivative propynal in the cold cloud TMC-1, with an abundance that is very close to that for the related species tricarbon monoxide, is reported. Propadienone, an isomer of propynal, was not detected and is hence less abundant than either C3O or HC2CHO.
The optimization of the wave functions is considered for coupled vibrations represented by linear combinations of products of functions depending only on a single vibrational coordinate. The functions themselves are optimized as well as configuration list. For the H2O molecule highly accurate results are obtained for the lowest 15 levels using significantly shorter expansions than would otherwise be possible.
We report the results of a series of calculations of state-to-state integral cross sections for collisions between O and nonvibrating H2O in the gas phase on a model nonreactive potential energy surface. The dynamical methods used include converged quantum mechanical scattering calculations, the j(z) conserving centrifugal sudden (j(z)-CCS) approximation, and quasi-classical trajectory (QCT) calculations. We consider three total energies 0.001, 0.002, and 0.005 E(h) and the nine initial states with rotational angular momentum less than or equal to 2 (h/2 pi). The j(z)-CCS approximation gives good results, while the QCT method can be quite unreliable for transitions to specific rotational sublevels. However, the QCT cross sections summed over final sublevels and averaged over initial sublevels are in better agreement with the quantum results.
A detailed description of the polycyclic aromatic hydrocarbon (PAH)/unidentified infrared band (UIR) mechanism is presented in which experimental spectral bandshape functions are used to simulate IR emission spectra for individual molecules. These spectra are additively superimposed to produce a conglomerate spectrum representative of a family of PAH molecules. Ab initio vibrational frequencies and intensities for nine PAHs (neutral and cationic) as large as ovalene are used in conjunction with measured bandshape and temperature-dependent redshift data to simulate the UIR bands. The calculated spectra of cations provide a closer match to the UIRs than do those of the neutrals. However, the PAH cations used in the simulations fail to reproduce the details of the UIR emission spectra. The discrepancies are potentially alleviated if both larger PAHs and a greater number of PAHs were included in the simulation.
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Results of observations of the carbon star TX Psc at high resolution in the 4000/cm spectral region and at moderate resolution from 2500 to 8000/cm are reported. The opacity sampling technique is employed to present model atmospheres of carbon stars with normal solar oxygen abundance and deep envelope composition that include HCN and C2H2. The oxygen abundance of TX Psc is found to be more accurately represented by a deep envelope composition depleted in oxygen by roughly two orders of magnitude than by a solar oxygen abundance. Polyatomic opacities influence the CO line depths and the derived oxygen abundance as a second-order effect. Polyatomic bands appear to be far too strong in the models, implying the need for another source of opacity to backwarm the outer atmosphere and thereby limit the polyatomic band depths. Dust, rather than polyatomic molecules, is a candidate for the backwarming opacity.
Simple group theoretical principles are applied to the consideration of electron scattering off atoms and diatomic and polyatomic molecules. This approach is also used to estimate relative strengths of electron-impact-induced transitions of diatomic and polyatomic molecules.
Comparisons between experimental and theoretical values of the thermal conductivity for a series of nonpolar polyatomic gases show large discrepancies at higher temperatures where the vibrational contribution becomes increasingly important. Examination of various theoretical approaches indicates that the discrepancies can be attributed to approximating the coefficient characterizing the diffusion of vibrational energy, D sub vib, by the self-diffusion coefficient. The present theories cannot accurately predict D sub vib, and its measurement is extremely difficult. Consequently, the approach adopted by the author is to obtain D sub vib by using experimental values of the thermal conductivity. An attempt is made to correlate these values of D sub vib with vibrational relaxation time, so that values of D sub vib can be obtained for all nonpolar polyatomic gases.
Light absorbing molecules and lasing molecules were discussed with regard to satisfying the following criteria for blackbody transfer lasers: (1) Good absorbers of blackbody radiation at 1500-2000 K; (2) Near resonant energy transfer from the absorbing gas to the lasant, provided not too many quantum number changes are required; (3) Dipole-dipole interactions for most efficient energy transfer; (4) Exothermic forward transfer reaction; (5) Polyatomic lasant molecules with at least two fundamental vibrational modes to ensure one or more states between the upper laser level and the ground state; (6) Polyatomic lasant molecules should not be so large or so complex that fast V-V relaxation occurs; (7) Metastable upper laser level for maintaining inversion, at least with respect to radiative and V-V decay; (8) Fast V-V into the upper laser level and out of the lower laser level; and (9) Lasing wavelengths less than 10.6 microns. Possible combinations of absorbers and lasants satisfying these criteria were discussed.
Basic formulations, analyses, and numerical procedures are presented to investigate radiative heat interactions in diatomic and polyatomic gases under local and nonlocal thermodynamic equilibrium conditions. Essential governing equations are presented for both gray and nongray gases. Information is provided on absorption models, relaxation times, and transfer equations. Radiative flux equations are developed which are applicable under local and nonlocal thermodynamic equilibrium conditions. The problem is solved for fully developed laminar incompressible flows between two parallel plates under the boundary condition of a uniform surface heat flux. For specific applications, three diatomic and three polyatomic gases are considered. The results are obtained numerically by employing the method of variation of parameters. The results are compared under local and nonlocal thermodynamic equilibrium conditions at different temperature and pressure conditions. Both gray and nongray studies are conducted extensively for all molecular gases considered. The particular gases selected for this investigation are CO, NO, OH, CO2, H2O, and CH4. The temperature and pressure range considered are 300-2000 K and 0.1-10 atmosphere, respectively. In general, results demonstrate that the gray gas approximation overestimates the effect of radiative interaction for all conditions. The conditions of NLTE, however, result in underestimation of radiative interactions. The method developed for this study can be extended to solve complex problems of radiative heat transfer involving nonequilibrium phenomena.
A study is made of the advantages that can be realized in compressible-flow research by employing a substitute heavy gas in place of air. The present report is based on the idea that by properly mixing a heavy monatomic gas with a suitable heavy polyatomic gas, it is possible to obtain a heavy gas mixture which has the correct ratio of specific heats and which is nontoxic, nonflammable, thermally stable, chemically inert, and comprised of commercially available components. Calculations were made of wind-tunnel characteristics for 63 gas pairs comprising 21 different polyatomic gases properly mixed with each of three monatomic gases (argon, krypton, and zenon).
Kinetic theory of nonspherical molecules - solutions for boltzmann equations and transport coefficients for inelastic polyatomic collisions
Values of the bond dissociation energies, ionization potentials, and electron affinities that were taken from the literature are presented in tables for some monatomic, diatomic, and polyatomic molecules which are found in many high-temperature chemical reactions including combustion reactions. Much of the information came from literature published after 1950 which either reported experimental and theoretical energy values or gave a review of previous literature on the subject. In some cases values for the bond dissociation energies were calculated from recently published heats of formation.
Viscosities and thermal conductivities, suitable for heat-transfer calculations, were estimated for about 200 gases in the ground state from 100 to 5000 K and 1-atmosphere pressure. Free radicals were included, but excited states and ions were not. Calculations for the transport coefficients were based upon the Lennard-Jones (12-6) potential for all gases. This potential was selected because: (1) It is one of the most realistic models available and (2) intermolecular force constants can be estimated from physical properties or by other techniques when experimental data are not available; such methods for estimating force constants are not as readily available for other potentials. When experimental viscosity data were available, they were used to obtain the force constants; otherwise the constants were estimated. These constants were then used to calculate both the viscosities and thermal conductivities tabulated in this report. For thermal conductivities of polyatomic gases an Eucken-type correction was made to correct for exchange between internal and translational energies. Though this correction may be rather poor at low temperatures, it becomes more satisfactory with increasing temperature. It was not possible to obtain force constants from experimental thermal conductivity data except for the inert atoms, because most conductivity data are available at low temperatures only (200 to 400 K), the temperature range where the Eucken correction is probably most in error. However, if the same set of force constants is used for both viscosity and thermal conductivity, there is a large degree of cancellation of error when these properties are used in heat-transfer equations such as the Dittus-Boelter equation. It is therefore concluded that the properties tabulated in this report are suitable for heat-transfer calculations of gaseous systems.