Search NASA⌕ Search

SEARCH · Search NASA

Results for “atomic theory”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 379 records · Page 21
All sourcesNASA NTRSDOE OSTI
NASA NTRS1974

Vibration-translation energy transfer in anharmonic diatomic molecules. 1: A critical evaluation of the semiclassical approximation

The semiclassical approximation is applied to anharmonic diatomic oscillators in excited initial states. Multistate numerical solutions giving the vibrational transition probabilities for collinear collisions with an inert atom are compared with equivalent, exact quantum-mechanical calculations. Several symmetrization methods are shown to correlate accurately the predictions of both theories for all initial states, transitions, and molecular types tested, but only if coupling of the oscillator motion and the classical trajectory of the incident particle is considered. In anharmonic heteronuclear molecules, the customary semiclassical method of computing the classical trajectory independently leads to transition probabilities with anomalous low-energy resonances. Proper accounting of the effects of oscillator compression and recoil on the incident particle trajectory removes the anomalies and restores the applicability of the semiclassical approximation.

Mckenzie, R. L.↗
NASA NTRS1975

Vibration-translation energy transfer in anharmonic diatomic molecules. I - A comparative evaluation of the semiclassical approximation

The semiclassical approximation (quantum oscillator, classical path) is applied to anharmonic diatomic oscillators in excited initial states. Multistate numerical solutions giving the vibrational transition probabilities for collinear collisions with an inert atom are compared with equivalent, exact quantum-mechanical calculations. Several symmetrization methods are shown to correlate accurately the predictions of both theories for all initial states, transitions, and molecular types tested, but only if coupling of the oscillator motion and the classical trajectory of the incident particle is considered. In anharmonic heteronuclear molecules, the customary semiclassical method of computing the classical trajectory independently leads to transition probabilities with anomalous low-energy resonances. Proper accounting of the effects of oscillator compression and recoil on the incident particle trajectory removes the anomalies and restores the applicability of the semiclassical approximation.

Mckenzie, R. L.↗
NASA NTRS1984

Basic governing equations for the flight regimes of aeroassisted orbital transfer vehicles

The basic governing equations for the low-density, high-enthalpy flow regimes expected in the shock layers over the heat shields of the proposed aeroassisted orbital transfer vehicles are derived by combining and extending existing theories. The conservation equations are derived from gas kinetic principles for a four-component ionized gas consisting of neutral molecules, neutral atoms, singly ionized ions, and electrons, assuming a continuum flow. The differences among translational-rotational, vibrational, and electron temperatures are accounted for, as well as chemical nonequilibrium and electric-charge separation. Expressions for convective and viscous fluxes, transport properties, and the terms representing interactions among various energy modes are given explicitly. The expressions for the rate of electron-vibration energy transfer, which violates the Landau-Teller conditions, is derived by solving the system of master equations accounting for the multiple-level transitions.

Lee, J.-H.↗
NASA NTRS1985

Basic Governing Equations for the Flight Regimes of Aeroassisted Orbital Transfer Vehicles

The basic governing equations for the low-density, high-enthalpy flow regimes expected in the shock layers over the heat shields of the proposed aeroassisted orbital transfer vehicles are derived by combining and extending existing theories. The conservation equations are derived from gas kinetic principles for a four-component ionized gas consisting of neutral molecules, neutral atoms, singly ionized ions, and electrons, assuming a continuum flow. The differences among translational-rotational, vibrational, and electron temperatures are accounted for, as well as chemical nonequilibrium and electric-charge separation. Expressions for convective and viscous fluxes, transport properties, and the terms representing interactions among various energy modes are explicitly given. The expressions for the rate of electron-vibration energy transfer, which violates the Landau-Teller conditions, are derived by solving the system of master equations accounting for the multiple-level transitions.

Lee, Jong-Hun↗
NASA NTRS2003

Iron catalyst chemistry in modeling a high-pressure carbon monoxide nanotube reactor

The high-pressure carbon monoxide (HiPco) technique for producing single-wall carbon nanotubes (SWNTs) is analyzed with the use of a chemical reaction model coupled with flow properties calculated along streamlines, calculated by the FLUENT code for pure carbon monoxide. Cold iron pentacarbonyl, diluted in CO at about 30 atmospheres, is injected into a conical mixing zone, where hot CO is also introduced via three jets at 30 degrees with respect to the axis. Hot CO decomposes the Fe(CO)5 to release atomic Fe. Then iron nucleates and forms clusters that catalyze the formation of SWNTs by a disproportionation reaction (Boudouard) of CO on Fe-containing clusters. Alternative nucleation rates are estimated from the theory of hard sphere collision dynamics with an activation energy barrier. The rate coefficient for carbon nanotube growth is estimated from activation energies in the literature. The calculated growth was found be about an order of magnitude greater than measured, regardless of the nucleation rate. A study of cluster formation in an incubation zone prior to injection into the reactor shows that direct dimer formation from Fe atoms is not as important as formation via an exchange reaction of Fe with CO in FeCO.

Evaluation Studies↗
NASA NTRS1994

Simulation of Tip-Sample Interaction in the Atomic Force Microscope

Recent simulations of the interaction between planar surfaces and model Atomic Force Microscope (AFM) tips have suggested that there are conditions under which the tip may become unstable and 'avalanche' toward the sample surface. Here we investigate via computer simulation the stability of a variety of model AFM tip configurations with respect to the avalanche transition for a number of fcc metals. We perform Monte-Carlo simulations at room temperature using the Equivalent Crystal Theory (ECT) of Smith and Banerjea. Results are compared with recent experimental results as well as with our earlier work on the avalanche of parallel planar surfaces. Our results on a model single-atom tip are in excellent agreement with recent experiments on tunneling through mechanically-controlled break junctions.

Good, Brian S.↗
NASA NTRS1974

Mariner 6, 7, and 9 ultraviolet spectrometer experiment - Analysis of hydrogen Lyman alpha data

Four Lyman alpha airglow measurements of the limb and disk of Mars, made by ultraviolet spectrometers on Mariner 6 and 7 in 1969 and Mariner 9 in 1971, are analyzed to determine the amount and distribution of atomic hydrogen above 80 km. The variation of atomic hydrogen with altitude is calculated by using time-independent chemical diffusion models from 80 to 250 km, and an exospheric model is used above 250 km. By employing radiative transfer theory that includes effects of pure absorption and accounts for temperature variations in the atmosphere, a spherical model of the airglow Lyman alpha emission is used to produce theoretical intensities for comparison with the data. It is found that (1) the exospheric temperature and distribution in 1971 are consistent with those determined in 1969, (2) the vertical optical depth above 80 km was 2.2 in 1969 and 5 in 1971, and (3) the derived atomic hydrogen distribution from 80 to 250 km requires a source of atomic hydrogen above 80 km. Comparison of observed profiles with chemical diffusion models implies a large downward flow of atomic hydrogen at 80 km coupled with a large upward flow of molecular hydrogen.-

Anderson, D. E., Jr.↗
NASA NTRS2006

Numerical Modeling of Turbulence Effects within an Evaporating Droplet in Atomizing Sprays

A new approach to account for finite thermal conductivity and turbulence effects within atomizing liquid sprays is presented in this paper. The model is an extension of the T-blob and T-TAB atomization/spray model of Trinh and Chen (2005). This finite conductivity model is based on the two-temperature film theory, where the turbulence characteristics of the droplet are used to estimate the effective thermal diffhsivity within the droplet phase. Both one-way and two-way coupled calculations were performed to investigate the performance of this model. The current evaporation model is incorporated into the T-blob atomization model of Trinh and Chen (2005) and implemented in an existing CFD Eulerian-Lagrangian two-way coupling numerical scheme. Validation studies were carried out by comparing with available evaporating atomization spray experimental data in terms of jet penetration, temperature field, and droplet SMD distribution within the spray. Validation results indicate the superiority of the finite-conductivity model in low speed parallel flow evaporating spray.

Balasubramanyam, M. S.↗
NASA NTRSDate not supplied

Modeling Ring-Opening Polymerization with Machine-Learned Committors

Many important industrial and biological processes depend on ring-opening polymerization (ROP), including large-scale production polymers, such as nylon 6, and a variety of biodegradable polymers and high-performance resins. Large-scale simulations (>200K atoms) of ROP were performed using a deep neural network-based method that captured the effect of the local chemical environment of the reactive sites using training data from quantum chemical methods. The utility of this method was demonstrated by modeling the cationic ROP of bis-benzoxazine, a promising resin for use in advanced high-temperature application composites (>200°C). Density functional theory calculations were used to map out the various ring opening and polymerization reaction paths that occur during the thermal processing of bis-benzoxazine. The probabilities of these reactions, as a function of local atomic configurations, were used to construct committor functions using a neural network approach. The learned committor functions were then used to determine when a particular reaction occurred within the REACTER framework for reactive molecular dynamics simulations. The experimentally observed exotherm that occurs during bis-benzoxazine ROP was captured in an effective manner in the simulations by imposing a local heating of the system that corresponds to the enthalpy of reaction for each reaction. The dependence of the final polymer morphology on the ROP reaction temperature was analyzed at the molecular scale. The results presented in this work indicate that machine-learned committor functions are a promising approach for incorporating high-fidelity reactivity criteria that capture the effect of local chemical environments into large-scale polymerization simulations.

machine learning, polymer simulations, molecular d↗
NASA NTRS1975

Effects of plasma microfields on radiative transitions from atomic levels above the ionization threshold

The effects of plasma electric microfields on line-like optical features arising from atomic levels above the ionization threshold are investigated within the framework of the quasi-static and single-frequency dynamic-field theories of spectral-line broadening. The 2p(23)P to 1s2p(3)P and 2s2p(3)P to 1s2s(3)S transitions in helium and helium-like ions are treated as examples. The mixing of the doubly excited levels in the perturbing microfields produces Stark broadening of the emission lines and induces autoionization of the 2p(23)P level, which, unlike the 2s2p(3)P level, is metastable against autoionization in the field-free environment. Determination of the complete Stark-broadening profiles in thermal plasmas is complicated by the need to include the effects of both the (quasi-static) ion and the (dynamic) electron fields. Under nonequilibrium conditions, where electric fields from either electron or ion plasma waves can far exceed nearby particle fields, the calculation and interpretation of the line shapes may be simplified and could provide a diagnostic probe of the wave-field properties.

Davis, J.↗
NASA NTRS1979

Relativistic L -shell Auger and Coster-Kronig rates and fluorescence yields

Relativistic calculations of radiationless transition rates to L -subshell vacancy states in selected atoms with Z in the 70-96 range have been performed. The Auger and Coster-Kronig transition probabilities are calculated from perturbation theory, assuming frozen orbitals, in the Dirac-Hartree-Slater approach. Transition rates, fluorescence yields, and Coster-Kronig yields are compared with nonrelativistic theoretical results and with experiment. Relativity is found to affect the L -subshell Auger widths by (10-25)% and individual transition rates to certain j-j configurations by as much as 40% at Z = 80. The widths of L sub i vacancy states and the L sub 2 Coster-Kronig yields f33 from these relativistic calculations agree much better with experiment than earlier nonrelativistic theoretical values.

Chen, M. H.↗
NASA NTRS1981

Atomic hydrogen rocket engine

A rocket using atomic hydrogen propellant is discussed. An essential feature of the proposed engine is that the atomic hydrogen fuel is used as it is produced, thus eliminating the necessity of storage. The atomic hydrogen flows into a combustion chamber and recombines, producing high velocity molecular hydrogen which flows out an exhaust port. Standard thermodynamics, kinetic theory and wall recombination cross-sections are used to predict a thrust of approximately 1.4 N for a RF hydrogen flow rate of 4 x 10 to the 22nd/sec. Specific impulses are nominally from 1000 to 2000 sec. It is predicted that thrusts on the order of one Newton and specific impulses of up to 2200 sec are attainable with nominal RF discharge fluxes on the order of 10 to the 22nd atoms/sec; further refinements will probably not alter these predictions by more than a factor of two.

Etters, R. D.↗
NASA NTRS1985

The O2 atmospheric 0-0 band and related emissions at night from Spacelab 1

A comparison of theoretically determined and measured O2 atmospheric (0-0) band intensities is presented. In view of suggestions that the O2 atmospheric emission and the atomic oxygen O(1S) emission both arise from the same intermediate state of O2, the measured 5577 A emission is also compared with theory; a similar comparison is made for the Herzberg bands of O2. It is concluded that the theories explaining these emissions do not yet provide a consistent picture.

Torr, M. R.↗
NASA NTRS1988

Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1990

Theoretical characterization of the 5Pi and 3Pi potential energy surfaces for NH + O yields N + OH

The reactant, product, and saddle point regions of the 5Pi and 3Pi potential energy surfaces for the reaction NH + O yields N + OH have been characterized using complete active space self consistent field/externally contracted configuration interaction calculations with large atomic natural orbital basis sets. The computed barrier heights are 5.6 and 11.7 kcal/mol on the 5Pi and 3Pi surfaces, respectively. Transition state theory with an Eckart tunneling correction is used to estimate the rate constant on the 5Pi surface.

Walch, Stephen P.↗
NASA NTRS1989

Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F + H2 yields HF + H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.

Bauschlicher, Charles W., Jr.↗