Engineering topics

Arnold, James O.

Publications and source records attributed to Arnold, James O..

At least 127 records · Page 7

NASA NTRS1996

NEQAIR96,Nonequilibrium and Equilibrium Radiative Transport and Spectra Program: User's Manual

This document is the User's Manual for a new version of the NEQAIR computer program, NEQAIR96. The program is a line-by-line and a line-of-sight code. It calculates the emission and absorption spectra for atomic and diatomic molecules and the transport of radiation through a nonuniform gas mixture to a surface. The program has been rewritten to make it easy to use, run faster, and include many run-time options that tailor a calculation to the user's requirements. The accuracy and capability have also been improved by including the rotational Hamiltonian matrix formalism for calculating rotational energy levels and Hoenl-London factors for dipole and spin-allowed singlet, doublet, triplet, and quartet transitions. Three sample cases are also included to help the user become familiar with the steps taken to produce a spectrum. A new user interface is included that uses check location, to select run-time options and to enter selected run data, making NEQAIR96 easier to use than the older versions of the code. The ease of its use and the speed of its algorithms make NEQAIR96 a valuable educational code as well as a practical spectroscopic prediction and diagnostic code.

Whiting, Ellis E.↗

NASA NTRS1996

Is the c State of CH2 Linear or Bent?

The c state of CH2 is found to be bent at the highest levels of theory used in this work, but the energy difference between the linear and bent geometries is only about 10 cm(exp -1). Improving the basis set or correlation treatment favor the linear geometry over the bent, thus it is impossible to definitively determine if the c state has a barrier in its bending potential.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

On the Photoelectron Spectra of Li4

The most stable structure for Li4(-) is found to be the rhombus. Electron detachment from this structure does not seem able to fully explain the photoelectron spectra. The computed results are consistent with those Rao, Jena, and Ray who have proposed that the experimental spectra consists of a superposition of detachment from the Li4(-) rhombus and tetrahedron, forming the singlet and triplet states of Li4, respectively.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

The Structure and Stability of B(n)H(+) Clusters

The geometries of the B(n)H(+) clusters for n=1-13 have been optimized at the B3LYP level of theory. Excluding B2H(+) all clusters are low-spin coupled. The structures appear to be related to the bare B(+)(n) clusters in two ways: 1) an H atom is added to the B(+)(n) cluster or 2) a BH is added to the B(+)(n-1) cluster. The B(+)(n)-H binding energies are computed at the B3LYP level of theory, and calibrated n using the CCSD(T) level of theory. The computed results tend to fall between the experimental best estimates and the experimental lower bounds. The B(+)(n)-H binding energies show an inverse correspondence with the B+(n-1)-B values) while the B(+)(n-1)-B and B(+)(n-1)-BH results tend to parallel each other.

Ricca, Alessandra↗

NASA NTRS1996

Chemical Storage of Data

We investigate the possibility of storing data using H and F on a polymer to signify 0 and 1 bits. We show that the difference between the B-F and B-H interaction energies for either C5H5B or C3H3N2B is only slightly larger than the variation in B-F interaction energy with type of neighboring atoms. Pyridine (C5H5N) and (CH3)3P=O have a much larger difference in the H and F interaction energies. (CH3)3P=O may be better suited as a surface probe, because the interaction with neighboring data sites should be smaller.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

On the Reaction of FNO2 with CH3, t-butyl, and C13H21

Theoretical studies are reported for the reaction of FN02 with the radicals CH3, t-butyl, and C13H21, which are templates for the radical site of a hydrogenated diamond surface. All structures axe fully optimized using density functional theory (DFT) based on the B3LYP functional. Calibration calculations axe performed for CH3 + FNO2 using the coupled cluster approach, the the internally contracted multireference configuration. interaction method, and second order perturbation theory based upon complete active space SCF (CASSCF) reference wave function. These calibration calculations support the B3LYP approach for the calculation of bond energies, but show the B3LYP barrier is too low. Combining the calibration calculations with the larger clusters yields our best estimate of a barrier of about 10 kcal/mol. for the reaction of FNO2 with a radical site on hydrogenated diamond.

Thuemmel, H. T.↗

NASA NTRS1996

Chemistry by Way of Density Functional Theory

In this work we demonstrate that density functional theory (DFT) methods make an important contribution to understanding chemical systems and are an important additional method for the computational chemist. We report calibration calculations obtained with different functionals for the 55 G2 molecules to justify our selection of the B3LYP functional. We show that accurate geometries and vibrational frequencies obtained at the B3LYP level can be combined with traditional methods to simplify the calculation of accurate heats of formation. We illustrate the application of the B3LYP approach to a variety of chemical problems from the vibrational frequencies of polycyclic aromatic hydrocarbons to transition metal systems. We show that the B3LYP method typically performs better than the MP2 method at a significantly lower computational cost. Thus the B3LYP method allows us to extend our studies to much larger systems while maintaining a high degree of accuracy. We show that for transition metal systems, the B3LYP bond energies are typically of sufficient accuracy that they can be used to explain experimental trends and even differentiate between different experimental values. We show that for boron clusters the B3LYP energetics are not as good as for many of the other systems presented, but even in this case the B3LYP approach is able to help understand the experimental trends.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

Thermal Protection Technology for Access to Space Vehicles

In the next century a new generation of space launch vehicles will be required to replace the Space Shuttle and the current expendable launch vehicle fleet. These new transportation systems must provide much lower lifecycle cost and mission versatility. In order to provide these attributes the vehicles must be designed with large operational margins of safety and weights comparable or lower than current systems. Advancements in Thermal Protection Systems (TPS) will be necessary to obtain these goals. This presentation will describe the thermal protection technology now under development by NASA that will be available for future Access to Space vehicles.

Goldstein, Howard E.↗

NASA NTRS1996

Infrared Spectra of Perdeuterated Naphthalene, Phenanthrene, Chrysene, and Pyrene

Calculations are carried out using density functional theory (DFT) to determine the harmonic frequencies and intensities of perdeuterated naphthalene, phenanthrene, pyrene, and chrysene. We also report matrix- isolation spectra for these four species. The theoretical and experimental frequencies and relative intensities for the perdeuterated species are in generally good agreement. The effect of perdeuteration is to reduce the sum of the integrated intensities by a factor of about 1.75. This reduction occurs for all vibrational motions, except for the weak low frequency ring deformation modes. There is also a significant redistribution of the relative intensities between the out-of-plane C-D bands relative to those found for the out-of-plane C-H bands. The theoretical isotopic ratios provide an excellent diagnostic of the degree of C-H(C-D) involvement in the vibrational bands, allowing in most cases a clear distinction of the type of motion.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

Displacement Energies for Nanorods

The geometries have been optimized and harmonic frequencies computed for three small hydrocarbon rods. The two lowest unique frequencies correspond to a torsion and a bend of the rods. The energy to bend or twist the rods has been computed by adding a fraction of the normal coordinate corresponding to these two modes to the equilibrium geometry. The density functional theory (using B3LYP) and self-consistent field (SCF) results are very similar for all properties considered.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

The Successive OH Binding Energies of Sc(OH)n+ for n=1-3

The geometries of Sc(OH)n+, for n = 1-3, have been optimized using density functional theory, in conjunction with the B3LYP hybrid functional. The zero-point energies are computed at the same level of theory. The successive OH bond energies have been computed at the CCSD(T) level for ScOH+ and Sc(OH)2+. The computed result for ScOD+ is in excellent agreement with the recent experiment of Armentrout and co-workers. There is a dramatic drop for the third OH, because Sc+ has only two valence electrons and therefore the bonding changes when the third OH is added. The difference between the B3LYP and CCSD(T) OH binding energies for the first two OH groups is discussed.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

The Calculation of Accurate Harmonic Frequencies of Large Molecules: The Polycyclic Aromatic Hydrocarbons, a Case Study

The vibrational frequencies and infrared intensities of naphthalene neutral and cation are studied at the self-consistent-field (SCF), second-order Moller-Plesset (MP2), and density functional theory (DFT) levels using a variety of one-particle basis sets. Very accurate frequencies can be obtained at the DFT level in conjunction with large basis sets if they are scaled with two factors, one for the C-H stretches and a second for all other modes. We also find remarkably good agreement at the B3LYP/4-31G level using only one scale factor. Unlike the neutral PAHs where all methods do reasonably well for the intensities, only the DFT results are accurate for the PAH cations. The failure of the SCF and MP2 methods is caused by symmetry breaking and an inability to describe charge delocalization. We present several interesting cases of symmetry breaking in this study. An assessment is made as to whether an ensemble of PAH neutrals or cations could account for the unidentified infrared bands observed in many astronomical sources.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

The Application B3LYP to Large Systems

The application of density functional theory (DFT), using the B3LYP functional, to a series of chemical problems is described. The first involves the calculation of silica-adsorbate bond energies, including both chemical bonds and weak hydrogen bonding. The calculation of vibrational frequencies for large organic systems is discussed. For the closed shell neutral systems, the B3LYP results are similar to the self- consistent- field results, however, for the positive ions, only the B3LYP level of theory is accurate and sufficiently inexpensive to allow the study of large systems. The final application involves the calculation of successive metal-ligand bond energies. The B3LYP bond energies and entropies are shown to be in good agreement with experiment.

Bauschlicher, Charles W.↗

NASA NTRS1996

The Application of DFT to Systems Containing Metal Atoms

The application of density functional theory (DFT) to a series of metal containing systems will be described. The focus will be on the calculation of accurate bond energies, especially metal-ligand successive bond energies. The DFT results will be compared with experiment and other levels of theory. If time permits, metal clusters will also be discussed.

Ricca, Alessandra↗

NASA NTRS1995

Capsule Aerothermodynamics. CFD Prediction Methodology; Database for CFD Validation; Capsule Flight Programs: AFE and Apollo Lessons Learned

Features of chemically reacting separated hypersonic flows are identified and issues concerning their analysis and simulation are discussed. Emphasis is placed on flows of high temperature dissociating and ionizing air and current methods for studying and characterizing these flows, including separation, are reviewed. The aeroassist orbital transfer vehicle and its flight trajectory are used for illustration. Thermochemical nonequilibrium phenomena are emphasized and extension of continuum analysis to the high altitude slip-flow regime is considered.

Deiwert, George S.↗

NASA NTRS1995

Ceramic Thermal Protection Technology From The Space Shuttle to Access to Space

The presentation will describe the Space Shuttle Orbiter Thermal Protection System. Ceramic materials technology developed for the Shuttle an improvements introduced after its early flights will be delineated. The current Thermal Protection Technology state of the art and future needs for low cost access to space will be discussed.

Goldstein, Howard E.↗

NASA NTRS1995

Two-Photon Laser-Induced Fluorescence O and N Atoms for the Study of Heterogeneous Catalysis in a Diffusion Reactor

Advanced laser-based diagnostics have been developed to examine catalytic effects and atom/surface interactions on thermal protection materials. This study establishes the feasibility of using laser-induced fluorescence for detection of O and N atom loss in a diffusion tube to measure surface catalytic activity. The experimental apparatus is versatile in that it allows fluorescence detection to be used for measuring species selective recombination coefficients as well as diffusion tube and microwave discharge diagnostics. Many of the potential sources of error in measuring atom recombination coefficients by this method have been identified and taken into account. These include scattered light, detector saturation, sample surface cleanliness, reactor design, gas pressure and composition, and selectivity of the laser probe. Recombination coefficients and their associated errors are reported for N and O atoms on a quartz surface at room temperature.

Pallix, Joan B.↗

NASA NTRS1995

Ames Research Center Mars/Pathfinder Heat Shield Design Verification ARC-JET Test

Design verification tests were performed on samples representing the aerobrake of the Mars/Pathfinder vehicle. The test specimens consisted of the SLA-561V ablator bonded to the honeycomb structure. The primary objective was to evaluate the ablation materials performance and to measure temperatures within the ablator, at the structural bondline and at the back sheet of the honeycomb structure. Other objectives were to evaluate the effect of ablative repair plug material treatment and voids in the heat shield. A total of 29 models were provided for testing in the Ames 60MW arc-jet facility. Of these, 23 models were flat-faced and six remaining models were curved edge ones, intended to simulate the conditions on the curved rim of the forebody where the maximum shear occurred. Eight sets of test conditions were used. The stagnation point heating rates varied from 47 to 240 W/cm2 and the stagnation pressures from 0.15 to 0.27 atm. (The maximum flight values are 132 W/cm2 and 0.25 atm) The majority of these runs were made at a nominal stagnation pressure of 0.25 atm. Two higher pressure runs were made to check the current (denser) ablation material for spallation, or other forms of thermal stress failure. Over 60% of the flatfaced models yielded good thermocouple data and all produced useful surface recession information. Of the five curved-edge models that were tested, only one gave good data; the remaining ones experienced model-holder failure. The test results can be summarized by noting that no failure of the ablative material was observed on any model. Also, the bondline temperature design limit of 250 C was never reached within an equivalent flight time despite a stagnation point heat load that exceeded the maximum flight value by up to 130%. At heating rates of over 200W/cm2 and stagnation pressures of 0.25 atm, or greater, the average surface recessions exceeded 0.5 cm on some models. The surface roughness increased dramatically at pressures above 0.25 atm and was four times greater at 0.27 atm than at 0.25 atm. Procured repair plug material performed much better than room-temperature cured plugs, as observed in the previous tests. Voids in the ablator did not increase local temperatures and gaps did not grow during testing.

Tran, Huy K.↗