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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
NASA NTRS1990

Dissociative recombination of molecular ions with electrons

An overview is presented for the present state of the art of laboratory measurements of the dissociative recombination of molecular ions with electrons. Most work has focussed on obtaining rates and their temperature dependence, as these are of primary interest for model calculations of ionospheres. A comparison of data obtained using the microwave afterglow method, the flowing afterglow technique, and the merged beam technique shows that generally the agreement is quite good, but there are some serious discrepancies, especially in the case of H(3+) recombination, that need to be resolved. Results of some earlier experimental work need to be reexamined in the light of more recent developments. Such cases are pointed out and a compilation of rate coefficients that have withstood scrutiny is presented. Recent advances in experimental methods, such as the use of laser-in-duced fluorescence, make it possible to identify some neutral products of dissociative recombination. What has been done so far and what results one might expect from future work are briefly reviewed.

Johnsen, Rainer↗
NASA NTRS1989

The dissociation energy of N2

The requirements for very accurate ab initio quantum chemical prediction of dissociation energies are examined using a detailed investigation of the nitrogen molecule. Although agreement with experiment to within 1 kcal/mol is not achieved even with the most elaborate multireference CI (configuration interaction) wave functions and largest basis sets currently feasible, it is possible to obtain agreement to within about 2 kcal/mol, or 1 percent of the dissociation energy. At this level it is necessary to account for core-valence correlation effects and to include up to h-type functions in the basis. The effect of i-type functions, the use of different reference configuration spaces, and basis set superposition error were also investigated. After discussing these results, the remaining sources of error in our best calculations are examined.

Almlof, Jan↗
NASA NTRS1989

Ab initio studies of dissociative recombination

Quantum chemical calculations of the dissociative recombination of O2(+) and N2(+) are reported. An approach for calculating autoionization widths from high-principal-quantum-number Rydberg states is summarized, and an example is presented for the lowest dissociative state of O2. For O2(+), the 1Sigma(+)u state is the sole source of O(1S) from the lowest 10 vibrational levels of the ion. Rate coefficients for generating O(1S) and O(1D) at ionospheric temperatures are reported.

Guberman, Steven L.↗
NASA NTRS1990

Dissociation and ionization of molecular gas in the spiral arms of M51

Researchers derive the star formation rate and efficiency in the arm and interarm regions of M51 from observations of the molecular (Lo et al. 1987) and ionized (van der Hulst et al. 1988) phases of the interstellar medium, and show that the HI observations of Tilanus and Allen (1989) are consistent with dissociation of molecular gas by these young, massive stars if n sub H greater than or equal to 200 cm (-2). However, these stars are not able to dissociate or ionize all the gas, and at least 60 percent must remain molecular in the interarm regions. The efficiency of star formation in M51 seems to be similar to that in the Galaxy, and does not appear to be enhanced in the spiral arms. Therefore, the effect of the strong density wave may be only to concentrate the gas, and hence the young stars, to the arm regions.

Lees, J. F.↗
NASA NTRS1991

Vibration-dissociation coupling in nonequilibrium flows

The purpose of the study is to evaluate all important physical phenomena contributing to the vibration-dissociation problem by developing a numerical technique for the simulation of the vibrational relaxation and dissociation/recombination of N(2) in an isothermal box. A set of coupled master equations representing each vibrational level of N(2) is solved, and both V-V and V-T exchanges between molecules and atoms are included, along with the effects of dissociation and recombustion from/to each level. It is observed that the inverse range parameter has a strong impact on the vibrational exchange rates and relaxation. In a heating case, the lower vibrational levels relax through a series of equilibrium distributions, while in a cooling case, a population inversion is formed in the upper levels. Other cases of heating and cooling will be simulated, and together with this work, used to develop a matrix of nonequilibrium relaxation runs.

Landrum, D. Brian↗
NASA NTRS1991

Theoretical study of the C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O

The successive C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O (ketene) are determined using large-basis sets and a high level of correlation treatment. For CH4, C2H2, and C2H4 the computed values are in excellent agreement with experiment. Using these results, the values 107.9 + or - 2.0 and 96.7 + or - 2.0 kcal/mol are recommended for the C-H bond dissociation energies of H2C2O and HC2O, respectively.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1991

Vibrational relaxation and dissociation in nitrogen

Calculations of the vibrational and dissociation transition probabilities are made for N2-N2 and N2-N collisions by means of a semiclassical N-state approximation. The flaws in previous techniques are reviewed, with special attention given to the prediction of overtones. The method presented ignores the effects of molecular rotation and employs a revised extended Rydberg intermolecular potential to describe diatom-diatom and diatom-atom collisions. The collision velocities investigated exhibit probabilities of less than unity by means of the N-state method. The continuum is quantized to treat dissociation, and the collision results demonstrate probability enhancements for V-V-T transitions in both bound-bound and bound-free transitions. The technique is of particular interest for the theoretical modeling of reentry flows such as those encountered in aerobraking maneuvers.

Varghese, Philip L.↗
NASA NTRS1991

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

The bond dissociation energies (De) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of De with respect to the one-particle basis is studied at the single-reference modified coupled-pair-functional (MCPF)level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration-interaction (MRCI) De values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size-extensive averaged-coupled-pair-functional (ACPF) method. The full-valence complete-active-space self-consistent-field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds.

Langhoff, Stephen R.↗
NASA NTRS1991

Electron impact excitation and dissociation of N2 via the b 1Pi(u) state

Electron impact excitation of the b 1Pi(u) state in N2 plays a prominent role in the dissociation of the molecule and thus in the production of atomic nitrogen in planetary atmospheres. Electron impact excitation cross sections combined with electron-impact-induced fluorescence measurements can yield the corresponding dissociation cross sections. Serious discrepancies exist among excitation cross sections reported in the literature. To clarify the situation, these cross sections were measured at two impact energies using electron energy loss spectroscopy. The new results are in agreement with recent values deduced from optical measurements and fall midway between previous results which are too high or low by factors of 2.

Ratliff, J. M.↗
NASA NTRS1989

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2.

Langhoff, Stephen R.↗
NASA NTRS1991

Fluid hydrogen at high density - Pressure dissociation

A model for the Helmholtz free energy of fluid hydrogen at high density and high temperature is developed. This model aims at describing both pressure and temperature dissociation and ionization and bears directly on equations of state of partially ionized plasmas, as encountered in astrophysical situations and high-pressure experiments. This paper focuses on a mixture of hydrogen atoms and molecules and is devoted to the study of the phenomenon of pressure dissociation at finite temperatures. In the present model, the strong interactions are described with realistic potentials and are computed with a modified Weeks-Chandler-Andersen fluid perturbation theory that reproduces Monte Carlo simulations to better than 3 percent. Theoretical Hugoniot curves derived from the model are in excellent agreement with experimental data.

Saumon, Didier↗
NASA NTRS1992

Dissociation energy of molecules in dense gases

A general approach is presented for calculating the reduction of the dissociation energy of diatomic molecules immersed in a dense (n = less than 10 exp 22/cu cm) gas of molecules and atoms. The dissociation energy of a molecule in a dense gas differs from that of the molecule in vacuum because the intermolecular forces change the intramolecular dynamics of the molecule, and, consequently, the energy of the molecular bond.

Kunc, J. A.↗
NASA NTRS1992

Viscosity of dissociating gases

Recent calculations of the viscosity of iodine suggest that existing predictions of viscosities of high-temperature (up to several thousands degrees) gases should be revised, with much more attention being paid to the atomic and molecular interactions in the gas. As the gas starts to dissociate, the frequency of atom-molecule and atom-atom interactions increases, and those collisions must be taken into account in calculations of viscosity at high temperature. In this study, the iodine is chosen as an example, and the dependence of its viscosity on the gas dissociation degree is shown. Several possible channels for I+I interaction are considered in addition to I+I2 and I2+I2 collisions, and the resulting collision integrals are averaged over all the important channels.

Kang, S. H.↗
NASA NTRS1992

Lyman alpha line shapes from electron impact H2 dissociative processes in the Jovian auroral zone

Over the past two years several Lyman alpha line profile spectra of Jupiter were obtained using the International Ultraviolet Explorer (IUE) telescope. Several different regions of the planet were observed including the auroral zone, the low and mid latitudes, and the equatorial region which includes the Lyman alpha bulge region. These results have presented a very interesting picture of atomic hydrogen on Jupiter with explanations that range from ion outflow in the auroral zone to large thermospheric winds at low and mid latitudes. New data are needed to address the outstanding questions. Almost certainly, high resolution spectra from the Hubble Space Telescope will play a role in new observations. Better data also require better models, and better models require new laboratory data as inputs. The purpose of this program is two-fold: (1) to introduce a method by which new laboratory electron impact measurements of H2 dissociation can be used to calculate both the slow and fast H(S-2) and H(P-2) fragments in an H2 atmosphere; and (2) to determine the predicted Lyman alpha line shape that would result from electron impact production of these dissociative fragments in the Jovian auroral zone.

Waite, J. H., Jr.↗
NASA NTRS1992

Vibration dissociation coupling in nonequilibrium flows

The final report on research between North Carolina State University and the NASA Ames Research Center is presented. The research was aimed at using the Schwartz, Slawsky, Herzfeld (SSH) theory to simulate the vibrational relaxation of nitrogen molecules undergoing dissociation or recombination over a wide range of conditions. The results of these simulations were then treated as exact, and they were used to develop a model for the coupled vibration-dissociation process. This new model is simple enough to be used in computational fluid dynamics codes, but still captures the physics of the complex process. The model is used to simulate the flow over typical geometries to test it and to determine how much impact it has on the flow field. The key elements of this research are summarized.

Candler, Graham V.↗
NASA NTRS1993

Vibration-dissociation coupling in CO, N2 and O2 - An evaluation of analytic transition rate expressions

Closed form expressions for inelastic state-to-state and state-specific dissociative rate coefficients for utilization in vibrational master equation studies of shock heated CO, N2, and O2 highly dilute in Ar are considered. The master equation is linearized by neglecting diatom-diatom collisions and recombination. Master equation results indicate that the most significant contribution to dissociation comes from low and mid lying vibrational levels.

Gonzales, David A.↗
NASA NTRS1993

Models for direct Monte Carlo simulation of coupled vibration-dissociation

A new model for reactive collisions is developed within the framework of a particle method, which simulates coupled vibration-dissociation (CVD) behavior in high-temperature gases. The fundamental principles of particle simulation methods are introduced with particular attention given to the probability functions employed to select thermal and reactive collisions. Reaction probability functions are derived which favor vibrationally excited molecules as reaction candidates. The new models derived here are used to simulate CVD behavior during thermochemical relaxation of constant-volume O2 reservoirs, as well as the dissociation incubation behavior of postshock N2 flows for comparisons with previous models and experimental data.

Haas, Brian L.↗
NASA NTRS1993

A preferential vibration dissociation coupling model for nonequilibrium flowfields

A preferential vibration-dissociation coupling model is incorporated into a radiatively coupled viscous shock laver code that also includes chemical, radiative, and thermal nonequilibrium. Stagnation point flow profiles are obtained for various Fire 2 flight conditions and for a typical 14 km/sec AOTV case, and comparisons are made with Fire 2 experimental data. Adjustments in molecular absorption coefficients are also made for several diatomic species. Based on comparisons with experimental data, very little preferential dissociation behavior is present in the Fire 2 flight conditions.

Mcgough, David E.↗