Engineering topics
Publications and source records attributed to Jaffe, R. L..
This paper represents an on-going effort at NASA Ames Research Center to develop a physics-based nonequilibrium model for hypersonic entry into the Martian atmosphere.
This paper represents a summary of results to date of an on-going effort at NASA Ames Research Center to develop a physics-based non-equilibrium model for hypersonic entry into the Martian atmosphere. Our approach is to first compute potential energy surfaces based on accurate solutions of the electronic Schroedinger equation and then use quasiclassical trajectory calculations to obtain reaction cross sections and rate coefficients based on these potentials. We have presented new rate coefficients for N2 dissociation and CO dissociation and exchange reactions. These results illustrate shortcomings with some of the rate coefficients in Parks original T-Tv model for Mars entries and with some of the 30-45 year old shock tube data. We observe that the shock tube experiments of CO + O dissociation did not adequately account for the exchange reaction that leads to formation of C + O2. This reaction is actually the primary channel for CO removal in the shock layer at temperatures below 10,000 K, because the reaction enthalpy for exchange is considerably lower than the comparable value for dissociation.
We study the no-slip boundary conditions for water at a hydrophobic (graphite) surface using non-equilibrium molecular-dynamics simulations. For the planar Couette flow, we find a slip length of 64 nm at 1 bar and 300 K, decreasing with increasing system pressure to a value of 31 nm at 1000 bar. Changing the properties of the interface to from hydrophobic to strongly hydrophilic reduces the slip to 14 nm. Finally, we study the flow of water past an array of carbon nanotubes mounted in an inline configuration with a spacing of 16.4 x 16.4 nm. For tube diameters of 1.25 and 2.50 nm we find drag coefficients in good agreement with the macroscopic, Navier-Stokes values. For carbon nanotubes, the no-slip condition is valid to within the definition of the position of the interface.
Single wall carbon nanotube (SWNT) bends, with diameters from approx. 1.0 to 2.5 nm and bend angles from 18 deg. to 34 deg., are observed in catalytic decomposition of hydrocarbons at 600 - 1200 C. An algorithm using molecular dynamics simulation (MD) techniques is developed to model these structures that are considered to be SWNT junctions formed by topological defects (i.e. pentagon-heptagon pairs). The algorithm is used to predict the tube helicities and defect configurations for bend junctions using the observed tube diameters and bend angles. The number and arrangement of the defects at the junction interfaces are found to depend on the tube helicities and bend angle. The structural and energetic calculations using the Brenner potential show a number of stable junction configurations for each bend angle with the 34 deg. bends being more stable than the others. Tight binding calculations for local density of state (LDOS) and transmission coefficients are carried out to investigate electrical properties of the bend junctions.
Molecular dynamics simulations of POE melts have been performed utilizing a potential force field parameterized to reproduce conformer energies and rotational energy barriers in dimethoxyethane as determined from ab initio electronic structure calculations. Chain conformations and dimensions of POE from the simulations were found to be in good agreement with predictions of a rotational isomeric state (RIS) model based upon the ab initio conformational. energies. The melt chains were found to be somewhat extended relative to chains at theta conditions. This effect will be discussed in light of neutron scattering experiments which indicate that POE chains are extended in the melt relative to theta solutions. The conformational characteristics of POE chains will also be compared with those of other poly (alkylethers), namely poly(oxymethylene), poly(oxytrimethylene) and poly(oxytetramethylene). Local conformational dynamics were found to be more rapid than in polymethylene. Calculated C-H vector correlation times were found to be in reasonable agreement with experimental values from C-13 NMR spin-lattice relaxation times. The influence of ionic salts on local conformations and dynamics will also be discussed.
Conformational energy contours of perfluoroalkanes, determined from ab initio calculations, confirm the well-known spitting of trans states into two minima at plus or minus 17 degrees but also show that the gauche states split as well, with minima at plus or minus 124 degrees and plus or minus 84 in order to relieve steric crowding. The directions of such split distortions from the perfectly staggered states are strongly coupled for adjacent pairs of bonds in a manner identical to the intradyad pair for poly (isobutylene) chains. These conformational characteristics are fully represented by a six-state rotational isomeric state (RIS) model for PTFE comprised of t(+), t(-), g(sup +)+, g(sup +)-, g(sup -) + and g(sup -)-states, located at the split energy minima. The resultant 6 x 6 statistical weight matrix is described by first-order interaction parameters for the g+(+) (ca. 0.6 kcal/mol) and g+- (ca. 2.0 kcal/mol) states, and second order parameters for the g(sup +)+g(sup +)+ (ca 0.6 kcal/mol) and g(sup +)+g(sup -)+ (ca. 1.0 kcal/mol) states. This six-state RIS model, without adjustment of the geometric or energy parameters as determined from the ab initio calculations, predicts the unperturbed chain dimensions and the fraction of gauche bonds as a function of temperature for PTFE in good agreement with available experimental values.
Ab initio quantum chemistry methods are used to study the energetics of interactions of O atoms with organic compounds. Polyethylene (CH2)n has been chosen as the model system to study the interactions of O(3P) and O(1D) atoms with polymers. In particular, H abstraction is investigated and polyethylene is represented by a C3 (propane) oligomeric model. The gradient method, as implemented in the GRADSCF package of programs, is used to determine the geometries and energies of products and reactants. The saddle point, barrier geometry is determined by minimizing the squares of the gradients of the potential with respect to the internal coordinates. To correctly describe the change in bonding during the reaction at least a two configuration MCSCF (multiconfiguration self consistent field) or GVB (generalized valence bond) wave function has to be used. Basis sets include standard Pople and Dunning sets, however, increased with polarization functions and diffuse p functions on both the C and O atoms. The latter is important due to the O(-) character of the wave function at the saddle point and products. Normal modes and vibrational energy levels are given for the reactants, saddle points and products. Finally, quantitative energetics are obtained by implementing a small CAS (complete active space) approach followed by limited configuration interaction (CI) calculations. Comparisons are made with available experimental data.
A comprehensive first-principles theoretical investigation of the gas phase reaction Ca + HF - CaF + H is reported. Ab initio potential energy calculations are first discussed, along with characteristics of the computed potential energy surface. Next, the fitting of the computed potential energy points to a suitable analytical functional form is described, and maps of the fitted potential surface are displayed. The methodology and results of a classical trajectory calculation utilizing the fitted potential surface are presented. Finally, the significance of the trajectory study results is discussed, and generalizations concerning dynamical aspects of Ca + HF scattering are drawn.
A computational study is reported on the A + BC - AB + C bimolecular exchange reaction in which BC is aligned with respect to the approach direction of atom A so that the initial rotational angular momentum vector of BC is either parallel (or equivalently antiparallel) or perpendicular to the initial velocity vector of A. The calculations employ a modification of the extended LEPS potential, which permits straightforward generation of noncollinear minimum energy reaction paths. The calculations clearly demonstrate that diatomic reagent alignment can markedly affect the nature of reaction product early partitioning; they also demonstrate that diatomic reagent alignment affects reactive cross sections.
In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.
Theoretical calculations of selected excitation energies and oscillator strengths for Ba are presented that overcome the difficulties of previous theoretical treatments. A relativistic effective-core potential treatment is used to account for the relativistic core contraction, but the outermost ten electrons are treated explicitly. Core-valence correlation can be included in this procedure in a rigorous and systematic way through a configuration-interaction calculation. Insight is gained into the importance of relativistic effects by repeating many of the calculations using an all-electron nonrelativistic treatment employing an extended Slater basis set. It is found that the intensity of the intercombination line 3P1-1S0 is accurately determined by accounting for the deviation from LS coupling through spin-orbit mixing with the 1P1 state, and that deviations from the Lande interval rule provide an accurate measure of the degree of mixing.
The structure, torsional potentials, vibrational spectra, and harmonic force fields for s-cis and s-trans isomers of methacryloyl fluoride are examined to understand the conformational properties of the molecules and their relationship to macroscopic polymer properties. The structure is found to be in good agreement with experiment. It is shown by calculations that the energy difference between the cis and the transisomers is less than 1 kcal/mol at both the split valence and the split valence polarized levels, with the trans form favored. Analysis of the torsional potentials indicates that a rigid rotor model provides a reasonable description of the motion of the COF group in the molecule. The torsional barrier to interconvert the s-trans to the s-cis form is found to be 7.0 kcal/mol. A fit of the data to a three-term Fourier series shows that it is possible to reproduce the experimentally derived barrier, even though a direct determination indicates that the barrier is higher.
An analysis of the radiative heating phenomena encountered during a typical aeroassisted orbital transfer vehicle (AOTV) trajectory was made to determine the potential impact of computational chemistry on AOTV design technology. Both equilibrium and nonequilibrium radiation mechanisms were considered. This analysis showed that computational chemistry can be used to predict (1) radiative intensity factors and spectroscopic data; (2) the excitation rates of both atoms and molecules; (3) high-temperature reaction rate constants for metathesis and charge exchange reactions; (4) particle ionization and neutralization rates and cross sections; and (5) spectral line widths.
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Introduction of partially localized orbitals is shown to reduce the number of terms needed to describe the bonding in transition metal clusters. Using this formalism, it is possible to compute the various intra- and inter-atomic electron correlation contributions to the bond energy. Calculations demonstrate the relative importance of several kinds of electron correlation terms involving the 3p, 3d, and 4s electrons. Improved interaction potentials are obtained for the dimers V(2) and Cr(2) when additional correlation is added to the CAS SCF results of Walch, Bauschlicher, Roos, and Nelin (1983).
The 1D-1S quadrupole transition probabilities for Ca, Sr and Ba have been computed using extended GTO and STO valence basis sets and configuration-interaction wavefunctions that include the important core-valence correlation effects. For Ba and Sr, the relativistic contraction of the core orbitals was accounted for in the GTO calculations by a relativistic effective-core potential. The computed Einstein coefficient for Ca of 39.6/s is in excellent agreement with the recent experimental value of 40 + or - 8/s. The best Einstein coefficients for Sr (44.7/s) and Ba (2.98/s) imply increasing quadrupole line strengths down the column. Relativistic effects substantially increase the quadrupole Einstein coefficient for Ba.
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Detailed line intensities of the rotational-vibrational spectrum of OH are calculated for various rates of population of sixteen bound vibrational levels in which the rotational level populations are in thermal equilibrium. The line intensities are convolved with the instrument function of the Visible Airglow Experiment on the AE C and E satellites to obtain spectra for comparison with the atmospheric data. Within the uncertainties, a model can be constructed that reproduces the observed spectrum. Synthetic spectra are computed for the OH Meinel system between 2000 A and 5.5 microns. The maximum intensity occurs between 1 micron and 2 microns.