Engineering topics

Langhoff, Stephen R.

Publications and source records attributed to Langhoff, Stephen R..

At least 37 records · Page 2

NASA NTRS1997

An Accurate Potential Energy Surface for H2O

We have carried out extensive high quality ab initio electronic structure calculations of the ground state potential energy surface (PES) and dipole moment function (DMF) for H2O. A small adjustment is made to the PES to improve the agreement of line positions from theory and experiment. The theoretical line positions are obtained from variational ro-vibrational calculations using the exact kinetic energy operator. For the lines being fitted, the root-mean-square error was reduced from 6.9 to 0.08 /cm. We were then able to match 30,092 of the 30,117 lines from the HITRAN 96 data base to theoretical lines, and 80% of the line positions differed less than 0.1 /cm. About 3% of the line positions in the experimental data base appear to be incorrect. Theory predicts the existence of many additional weak lines with intensities above the cutoff used in the data base. To obtain results of similar accuracy for HDO, a mass dependent correction to the PH is introduced and is parameterized by simultaneously fitting line positions for HDO and D2O. The mass dependent PH has good predictive value for T2O and HTO. Nonadiabatic effects are not explicitly included. Line strengths for vibrational bands summed over rotational levels usually agree well between theory and experiment, but individual line strengths can differ greatly. A high temperature line list containing about 380 million lines has been generated using the present PES and DMF

Schwenke, David W.↗

NASA NTRS1996

Properties of Diamond and Diamond-Like Clusters in Nanometric Dimensions

Variations in materials properties of small clusters of nanometric dimensions were investigated. Investigations were carried out for diamond and diamond-like particles in spherical shapes. Calculations were performed for clusters containing over 1000 carbon atoms. Results indicate that as the cluster size diminishes, (i) the average cohesive energy becomes weaker, (ii) the excess surface energy increases, and (iii) the value for stiffness decreases.

Halicioglu, Timur↗

NASA NTRS1996

Quantum Mechanical Determination of Potential Energy Surfaces for TiO and H2O

We discuss current ab initio methods for determining potential energy surfaces, in relation to the TiO and H2O molecules, both of which make important contributions to the opacity of oxygen-rich stars. For the TiO molecule we discuss the determination of the radiative lifetimes of the excited states and band oscillator strengths for both the triplet and singlet band systems. While the theoretical radiative lifetimes for TiO agree well with recent measurements, the band oscillator strengths differ significantly from those currently employed in opacity calculations. For the H2O molecule we discuss the current results for the potential energy and dipole moment ground state surfaces generated at NASA Ames. We show that it is necessary to account for such effects as core-valence Correlation energy to generate a PES of near spectroscopic accuracy. We also describe how we solve the ro-vibrational problem to obtain the line positions and intensities that are needed for opacity sampling.

Langhoff, Stephen R.↗

NASA NTRS1996

Towards the Synthesis and Identification of Tetrahedral N4

Tetrahedral (Td)-N4 has attracted attention as a high energy density material candidate. Although computational studies have shown Td-N4 to be a stable structure on the ground-state potential energy surface, it has yet to be experimentally observed. This study investigates possible synthetic pathways via excited state surfaces. Preliminary results include a comparison of vertical excitation energies from Td-N4 using CIS, CIS(D), CIS(3), LRCCSD, CASSCF, CASPT2, and MRCI ab initio methods. Previous studies have predicted weak IR vibrational intensities. Therefore, alternative detection schemes of Td-N4 are also investigated, such as UV and vibrational Raman spectroscopy.

Dateo, Christopher E.↗

NASA NTRS1996

An Ab Initio Based Potential Energy Surface for Water

We report a new determination of the water potential energy surface. A high quality ab initio potential energy surface (PES) and dipole moment function of water have been computed. This PES is empirically adjusted to improve the agreement between the computed line positions and those from the HITRAN 92 data base. The adjustment is small, nonetheless including an estimate of core (oxygen 1s) electron correlation greatly improves the agreement with experiment. Of the 27,245 assigned transitions in the HITRAN 92 data base for H2(O-16), the overall root mean square (rms) deviation between the computed and observed line positions is 0.125/cm. However the deviations do not correspond to a normal distribution: 69% of the lines have errors less than 0.05/cm. Overall, the agreement between the line intensities computed in the present work and those contained in the data base is quite good, however there are a significant number of line strengths which differ greatly.

Partridge, Harry↗

NASA NTRS1996

FEM R-Matrix Calculations of Electron-H2 Collisions

Electron-H2 Collisions have been studied using the finite-element R-matrix method. Our approach uses a mixed finite-element and Gaussian basis to describe the continuum electron. In the inner region, the multi-centered nature of the Gaussian basis provides an efficient representation in the regions of space near the nuclei, whereas the piecemeal and energy-independent nature of the FEM basis is particular well suited for R-matrix calculations. Fixed nuclei calculations have been carried out at 1.4 a(sub 0), the equilibrium internuclear distance of the ground state. Up to six target states are included: the X(sup 1)E+(sub g), b(sup 3)E+(sub u), a(sup 3)E+(sub g), B(sup 1)E+(sub u), c(sup 3)II(sub u), and C(sup 1)II(sub u) states, and configuration-interaction functions are used to describe the target states. The results will be compared with available theoretical and experimental data.

Huo, Winifred M.↗

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

Stress Calculations for Carbon Nanotubes

Atomic stresses were calculated for carbon nanotubes under strain conditions. Graphitic tubules with radii ranging from approximately 2 to 11 Angstroms and two different tubule structures with varying atomic orientations were included in the calculations. Elongations and contractions were applied in the axial direction and atomic stress values were calculated for infinitely long tubules. The calculations were carried out using Brenner's function which was developed for carbon species. Results indicate that the stress is tensile in the radial direction while it is compressive in the tangential direction. Variations in stress values in the direction of the cylindrical aids were investigated as a function of applied strain. Furthermore, using the stress-strain curve (calculated based on atomic considerations), the values of Young's modulus and Poisson's ratio for nanotubules were also estimated.

Halicioglu, Timur↗

NASA NTRS1996

Ab Initio Calculation of Accurate Vibrational Frequencies for Molecules of Interest in Atmospheric Chemistry

Due to advances in quantum mechanical methods over the last few years, it is now possible to determine ab initio potential energy surfaces in which fundamental vibrational frequencies are accurate to within +/- 8 cm(sup -1) on average, and molecular bond distances are accurate to within +/- 0.001-0.003 A, depending on the nature of the bond. That is, the potential energy surfaces have not been scaled or empirically adjusted in any way, showing that theoretical methods have progressed to the point of being useful in analyzing spectra that are not from a tightly controlled laboratory environment, such as rovibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy win be presented and discussed. These include the HNO, CH4, C2H4, and ClCN molecules. The HNO molecule is interesting due to the very large H-N anharmonicity, while ClCN has a very large Fermi resonance. The ab initio studies for the CH4 and C2H4 molecules present the first accurate full quartic force fields of any kind (i.e., whether theoretical or empirical) for a five-atom and six-atom system, respectively.

Lee, Timothy J.↗

NASA NTRS1996

Low-Energy Electron Impact Excitation of the (010) Bending Mode of CO2

Low-energy electron impact excitation of the fundamental modes of CO2 has been extensively studied, both experimentally and theoretically. Much attention has been paid to the virtual state feature in the the (100) mode excitation and the (sup 2)II(sub upsilon) resonance feature around 3.8 eV, which is observable in all three fundamental modes. For the excitation of the (010) mode away from the resonance region, the Born dipole approximation was generally considered adequate. The present study employs the Born dipole approximation to treat the long range interaction and the Schwinger multichannel method for the short range interaction. The roles of the two interaction potentials will be compared.

Huo, Winifred M.↗

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

Determination of Highly Accurate Heats of Formation

Two approaches for directly computing a molecular heat of formation based on sophisticated ab initio electronic structure theory axe discussed and example calculations are presented for several molecules of interest in atmospheric chemistry including HNO and CICN. The accuracy of these approaches for a small subset of the molecules is demonstrated by comparison to very accurate experimental data. A third approach for evaluating accurate heats of formation consists of combining experimental and theoretical data. The potential for this method to provide reliable thermochemical data on many molecules using accurate experimental beats of formation for only a small number of species is demonstrated by giving accurate (Delta)H(sup 0, sub f) quantities for a host of fluorine, chlorine, and bromine oxide and nitrogen oxide compounds. Potential pitfalls in all three approaches are discussed.

Lee, Timothy J.↗

NASA NTRS1996

Spectroscopic Measurement of the Flows in an Arc-Jet Facility

To provide the proper test conditions for various applications, the characteristics of arcjet test facilities should be known. To determine the operational characteristics of an arcjet facility, emission spectroscopy measurements have been performed and analyzed in a previous study. As an extension of the study, radiation from the free stream and the shock layer of 15 cm diameter blunt-body test articles is measured under different test conditions in the NASA Ames 20 MW Arcjet Facility. The test gas is a mixture of argon and air or N2 and argon. To capture the spatially resolved emission spectra along the stagnation streamline of the blunt-body, a CCD camera (1024 x 256 array) with .275 m Czerny-Turner spectrograph is used. The optical system is calibrated in situ using tungsten and deuterium radiation sources. The emission measurements supplement the existing data base and will help provide better understanding of the equilibration processes in the shock layer region.

Park, C. S.↗

NASA NTRS1995

The Study of the Successive Metal-Ligand Binding Energies for Fe(sup +), Fe(sup -), V(sup +) and Co(sup +)

The successive binding energies of CO and H2O to Fe(sup +), CO to Fe(sup -), and H2 to Co(sup +) and V(sup +) are presented. Overall the computed results are in good agreement with experiment. The trends in binding energies are analyzed in terms of metal to ligand donation, ligand to metal donation, ligand-ligand repulsion, and changes in the metal atom, such as hybridization, promotion, and spin multiplicity. The geometry and vibrational frequencies are also shown to be directly affected by these effects.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1995

The Low-Lying Electronic States of LiB

The spectroscopic constants for the triplet and singlet states of LiB below about 30 000/ cm are determined using an internally contracted multireference configuration interaction approach in conjunction with [6s 5p 3d 2f] atomic natural orbital basis sets. The ground state is (sup 3)Pi as found in previous work. No excited triplet states are found to be ideal for characterizing the ground state; the (1)(sup 3)Sigma(sup -) state has a transition energy that is too small for many experimental approaches and the (2)(sup 3)Pi and (3)(sup 3)Pi states have bond lengths that are significantly longer than the ground state, resulting in transition intensities that are spread out over many vibrational levels of the ground state.

Ricca, Alessandra↗

NASA NTRS1995

A Study of the X(sup 2) Sigma(sup +) and A(sup 2) Pi States of MgAr(sup +) and MgKr(sup +)

The ground (sup 2)Sigma(sup +) and lowest excited (sup 2)Pi states of MgAr(sup +) and MgKr(sup +) are studied using the singles and doubles configuration interaction (SDCI) approach, in conjunction with large basis sets. The effect of Mg core correlation and core polarization are accounted for using the core-polarization potential (CPP) approach. Franck-Condon factors, oscillator strengths, radiative lifetimes, dissociation energies, bond lengths, and excitation energies are reported. The computed results are in good agreement with the available experimental data.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1995

The G2(B3LYP/MP2/CC) Approach: A Modification of the G2(MP2) Approach and a Comparison with B3LYP Results

The quadratic configuration interaction calculation in the G2(MP2) approach is replaced by a coupled-cluster singles and doubles calculation including a perturbational estimate of the triples excitations. In addition, the SCF and MP2 geometry optimizations and SCF frequency calculation in the G2(MP2) approach are replaced by a B3LYP geometry optimization and frequency calculation in the proposed G2(B3LYP/MP2/CC) approach. This simplification does not affect the average absolute deviation from experiment, but decreases the maximum error compared with the G2(MP2) approach. The G2(B3LYP/MP2/CC) results are compared with those obtained using the B3LYP approach, and the G2(B3LYP/MP2/CC) model is found to be more reliable, even if the B3LYP calculations are performed using a large basis set.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1995

MP2 Studies of Relativistic Effects on the Linear Stationary Points of the H+Cl2 Yields HCl+Cl and Cl+HCl Yields ClH+Cl Reactions

The influence of relativistic effects on the linear stationary points of the potential energy surfaces of the ClHCl and HCl2 systems is studied. Scalar relativistic effects have little influence on the geometries and the energies of these points. Spin-orbit effects have no influence on the barrier of the forward reaction of H with Cl2, but increase the reaction energy. The total relativistic effect is an increase of the reaction energy by 2.3 kJ /mol. The barrier for the iso-energetic exchange reaction of HCl with Cl is decreased by 0.5 kJ /mol due to the scalar relativistic effects. This small decrease is cancelled by the larger increase of 2.5 kJ /mol due to spin-orbit effects, giving a total relativistic effect of 2.0 kJ /mol.

Visscher, L.↗