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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.

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At least 181 records · Page 10
All sourcesNASA NTRSDOE OSTI
NASA NTRS2001

Ab Initio and Improved Empirical Potentials for the Calculation of the Anharmonic Vibrational States and Intramolecular Mode Coupling of N-Methylacetamide

The second-order Moller-Plesset ab initio electronic structure method is used to compute points for the anharmonic mode-coupled potential energy surface of N-methylacetamide (NMA) in the trans(sub ct) configuration, including all degrees of freedom. The vibrational states and the spectroscopy are directly computed from this potential surface using the Correlation Corrected Vibrational Self-Consistent Field (CC-VSCF) method. The results are compared with CC-VSCF calculations using both the standard and improved empirical Amber-like force fields and available low temperature experimental matrix data. Analysis of our calculated spectroscopic results show that: (1) The excellent agreement between the ab initio CC-VSCF calculated frequencies and the experimental data suggest that the computed anharmonic potentials for N-methylacetamide are of a very high quality; (2) For most transitions, the vibrational frequencies obtained from the ab initio CC-VSCF method are superior to those obtained using the empirical CC-VSCF methods, when compared with experimental data. However, the improved empirical force field yields better agreement with the experimental frequencies as compared with a standard AMBER-type force field; (3) The empirical force field in particular overestimates anharmonic couplings for the amide-2 mode, the methyl asymmetric bending modes, the out-of-plane methyl bending modes, and the methyl distortions; (4) Disagreement between the ab initio and empirical anharmonic couplings is greater than the disagreement between the frequencies, and thus the anharmonic part of the empirical potential seems to be less accurate than the harmonic contribution;and (5) Both the empirical and ab initio CC-VSCF calculations predict a negligible anharmonic coupling between the amide-1 and other internal modes. The implication of this is that the intramolecular energy flow between the amide-1 and the other internal modes may be smaller than anticipated. These results may have important implications for the anharmonic force fields of peptides, for which N-methylacetamide is a model.

Gregurick, Susan K.↗
NASA NTRS1982

The rotational spectra of HCNH/+/ and COH/+/ from quantum mechanical calculations

A description is provided of ab initio molecular orbital calculations designed to provide accurate predictions for the J = 1 to 0 rotational line of the candidate interstellar molecules HCNH(+) and COH(+). The former is believed to be important in the formation of both HCN and HNC in the interstellar medium. The latter, a metastable isomer of HCO(+), was first proposed as an interstellar molecule by Herbst et al. (1976). Attention is given to thermochemical arguments that this molecule can be formed in the same reactions which are proposed to form HCO(+), taking into account theoretical data which establish its stability to intramolecular rearrangement. Rotational constants are derived by applying an empirical correction to the ab initio rotational constants.

Defrees, D. J.↗
NASA NTRS1995

Ab Initio Potential Energy Surfaces and the Calculation of Accurate Vibrational Frequencies

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 plus or minus 8 cm(exp -1) on average, and molecular bond distances are accurate to within plus or minus 0.001-0.003 Angstroms, 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 vibrational spectra from the interstellar medium. Some recent examples demonstrating this accuracy will 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 NTRS1981

Reactions of ground-state and metastable O/2+/ ions with He, O2, N2, and CO2 at thermal energies

Evidence is presented that some previous studies of reactions of O(2+) ions with various atoms and molecules referred to ion samples composed in part of ions in metastable (1D and/or 1S) states. This finding resolves the 3 orders of magnitude discrepancy between previous experimental and calculated rate coefficients for the O(2+)(3P) + He charge transfer process. Using a drift tube to distinguish, via arrival time differences, groundstate O(+)(3P) and metastable ions, a rate coefficient of (3.5 plus or minus 1.5) x 10 to the -11th cu cm/sec is obtained for the reaction, in good agreement with that obtained from ab initio theoretical calculations. Previous conclusions concerning reactions of O(2+) with O2 and N2, however, remain valid since the difference in reactivity of ground-state and metastable O(2+) ions appears to be negligible in this case. The rate coefficient for the reaction O(2+) + CO2 has been determined to be (2 plus or minus 0.5) x 10 to the -9th cu cm/sec for ions either in the ground-state or in metastable states.

Johnsen, R.↗
NASA NTRS1987

High temperature transport properties of air

A general computer code was developed to allow calculation of atom-atom and ion-atom transport collision integrals from accurate potential energy curves described by a set of discrete data points for a broad range of scattering conditions. This code is based upon semiclassical approximations that properly account for quantum mechanical behavior such as tunneling effects near a barrier maximum, resonance charge exchange, and nuclear symmetry effects. Transport collision integrals were determined for N-N, O-O, N(+)-N, and O(+)-O interactions from complete sets of accurate potential functions derived from combined experimental and ab initio structure calculations. For the O-O case, this includes results for excited states. The calculated values of the N(+)-N and O(+)-O resonance charge exchange cross section Q(ex) agree well with measurements from beam experiment that are available at high energies where the diffusion cross section Q(d) satisfies Q(d) approximately equal to 2Q(ex).

Levin, E.↗
NASA NTRS1991

The study of molecular spectroscopy by ab initio methods

This review illustrates the potential of theory for solving spectroscopic problems. The accuracy of approximate techniques for including electron correlation have been calibrated by comparison with full configuration-interaction calculations. Examples of the application of ab initio calculations to vibrational, rotational, and electronic spectroscopy are given. It is shown that the state-averaged, complete active space self-consistent field, multireference configuration-interaction procedure provides a good approach for treating several electronic states accurately in a common molecular orbital basis.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1974

Tentative identification of U93.174 as the molecular ion N2H/+/

On the basis of a consideration of the rotation constant and the hyperfine structure together with the results of an ab initio structural calculation it is suggested that the three closely space new interstellar lines near 93.174 GHz reported by Turner (1974) might have been produced by the molecular ion N2H(+). It is pointed out that the identification of N2H(+) is reasonable also in terms of current ideas of interstellar chemistry.

Green, S.↗
NASA NTRS1977

Comment of fitting ab initio intermolecular potentials for scattering calculations

The angular dependence of the interaction between two rigid linear rotors is considered, and one of the two expansions in current use is shown to be inappropriate. Interpolation of tabulated radial interactions is also discussed, and numerical tests are presented which demonstrate the accuracy of Lagrange and spline algorithms as a function of the spacing between points.

Green, S.↗
NASA NTRS1983

An ab initio study of core-valence correlation

Especially in the cases of the first two columns of the periodic table, the inclusion of core-valence correlation in ab initio CI calculations yields a contraction of the atomic valence shell and improves both calculated atomic ionization potentials and atomic energy separations. For the alkali dimers Na2, K2, and Rb2, the presently calculated bond lengths are in excellent agreement with experiments when core-valence is included. In addition, the valence dissociation energies are accurate.

Partridge, H.↗
NASA NTRS1987

Theoretical study of the dissociation energy and the red and violet band systems of CN

The dissociation energy (D sub O) of CN is determined to be 7.65 + or - 0.06 eV. This corresponds to delta H sub f (CN) = 105.3 + or - 1.5 kcal/mole, in excellent agreement with Engleman and Rouse (1975), but considerably larger than the recent value deduced from shock-tube studies by Colket (1984). The result is obtained not only from extensive ab initio MRCI calculations using a very large Gaussian basis set, but also from extrapolation of the directly computed value by comparison of computed and experimental results fo NO, C2, and N2. As an additional calibration of the methods, the D sub O value for CN was computed from the corresponding value for CN(-) using the experimental electron affinity data. The lifetime of the nu prime = 0 level of the violet (B 2 sigma + yields X 2 sigma +) system was computed to be 62.4 ns, in good agreement with both experiment and previous calculations. Lifetimes for the red (A 2 pi yields X 2 sigma +) system decrease with increasing nu prime, which is consistent both with the recent experiment and calculations. While the computed lifetimes are significantly longer that those obtained from the experiment, they are shorter than those deduced from an analysis of the solar spectrum. However the D sub O and f (sub OO) are consistent with Lambert's model for the solar spectrum.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1991

Theoretical and experimental studies relevant to interpretation of auroral emissions

The accomplishments achieved over the past year are detailed with emphasis on the interpretation or auroral emissions and studies of potential spacecraft-induced contamination effects. Accordingly, the research was divided into two tasks. The first task is designed to add to the understanding of space vehicle induced external contamination. An experimental facility for simulation of the external environment for a spacecraft in low earth orbit was developed. The facility was used to make laboratory measurements of important phenomena required for improving the understanding of the space vehicle induced external environment and its effect on measurement of auroral emissions from space-based platforms. A workshop was sponsored to provide a forum for presentation of the latest research by nationally recognized experts on space vehicle contamination and to discuss the impact of this research on future missions involving space-based platforms. The second task is to add an ab initio auroral calculation to the extant ionospheric/thermospheric global modeling capabilities. Once the addition of the code was complete, the combined model was to be used to compare the relative intensities and behavior of various emission sources (dayglow, aurora, etc.). Such studies are essential to an understanding of the types of vacuum ultraviolet (VUV) auroral images which are expected to be available within two years with the successful deployment of the Ultraviolet Imager (UVI) on the ISTP POLAR spacecraft. In anticipation of this, the second task includes support for meetings of the science working group for the UVI to discuss operational and data analysis needs. Taken together, the proposed tasks outline a course of study designed to make significant contributions to the field of space-based auroral imaging.

Keffer, Charles E.↗
NASA NTRS1991

Theoretical characterization of tetrahedral N4

Results are reported from ab initio theoretical calculations of the structure and energetics of tetrahedral N4. The theoretical basis and implementation of the computations are reviewed, and the results are presented in tables. It is found that a tetrahedral N4 molecule has energy 186 kcal/mole greater than that of two N2 molecules, with a 61-kcal/mole barrier between the two species. Brief consideration is given to the possible use of N4 (should a process for synthesizing it be developed) as a high-energy-density fuel for supersonic transport aircraft.

Lee, Timothy J.↗
NASA NTRS1994

Theoretical and experimental studies relevant to interpretation of auroral emissions

This report describes the accomplishments of a program designed to develop the tools necessary to interpret auroral emissions measured from a space-based platform. The research was divided into two major areas. The first area was a laboratory study designed to improve our understanding of the space vehicle external environment and how it will affect the space-based measurement of auroral emissions. Facilities have been setup and measurements taken to simulate the gas phase environment around a space vehicle; the radiation environment encountered by an orbiting vehicle that passes through the Earth's radiation belts; and the thermal environment of a vehicle in Earth orbit. The second major area of study was a modeling program to develop the capability of using auroral images at various wavelengths to infer the total energy influx and characteristic energy of the incident auroral particles. An ab initio auroral calculation has been added to the extant ionospheric/thermospheric global modeling capabilities within our group. Once the addition of the code was complete, the combined model was used to compare the relative intensities and behavior of various emission sources (dayglow, aurora, etc.). Attached papers included are: 'Laboratory Facility for Simulation of Vehicle-Environment Interactions'; 'Workshop on the Induced Environment of Space Station Freedom'; 'Radiation Damage Effects in Far Ultraviolet Filters and Substrates'; 'Radiation Damage Effects in Far Ultraviolet Filters, Thin Films, and Substrates'; 'Use of FUV Auroral Emissions as Diagnostic Indicators'; and 'Determination of Ionospheric Conductivities from FUV Auroral Emissions'.

Keffer, Charles E.↗
NASA NTRS1999

Collision-Induced Absorption by H2 Pairs in the Second Overtone Band at 298 and 77.5 K: Comparison between Experimental and Theoretical Results

The collision-induced spectra of hydrogen in the region of the second overtone at 0.8 microns have been recorded at temperatures of 298 and 77.5 K and for gas densities ranging from 100 to 800 amagats. The spectral profile defined by the absorption coefficient per squared density varies significantly with the density, so that the binary absorption coefficient has been determined by extrapolations to zero density of the measured profiles. Our extrapolated measurements and our recent ab initio quantum calculation are in relatively good agreement with one another. Taking into account the very weak absorption of the second overtone band, the agreement is, however, not as good as it has become (our) standard for strong bands.

Brodbeck, C.↗
NASA NTRS2002

Theoretical Study of Decomposition Pathways for HArF and HKrF

To provide theoretical insights into the stability and dynamics of the new rare gas compounds HArF and HKrF, reaction paths for decomposition processes HRgF to Rg + HF and HRgF to H + Rg + F (Rg = Ar, Kr) are calculated using ab initio electronic structure methods. The bending channels, HRgF to Rg + HF, are described by single-configurational MP2 and CCSD(T) electronic structure methods, while the linear decomposition paths, HRgF to H + Rg + F, require the use of multi-configurational wave functions that include dynamic correlation and are size extensive. HArF and HKrF molecules are found to be energetically stable with respect to atomic dissociation products (H + Rg + F) and separated by substantial energy barriers from Rg + HF products, which ensure their kinetic stability. The results are compatible with experimental data on these systems.

Chaban, Galina M.↗
NASA NTRS2007

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

electrolytes↗
NASA NTRS1991

Ab initio study of the electrostatic multipole nature of torsional potentials in CH3SSCH3, CH3SSH, and HOOH

The origin of torsional potentials in H3CSSCH3, H3CSSH, and HOOH and the anisotropy of the local charge distribution has been analyzed in terms of atomic multipoles calculated from the ab initio LCAO-MO-SCF wave function in the 6-31G* basis set. The results indicate that for longer -S-S-bonds the major contribution to these torsional barriers are electrostatic interactions of the atomic multipoles located on two atoms forming the rotated bond. This finding demonstrates the important role of electrostatic 1-2 interatomic interactions, usually neglected in conformational studies. It also opens the possibility to derive directly from accurate ab initio wave functions a simple nonempirical torsional potential involving atomic multipoles of two bonded atoms defining the torsional angle. For shorter -O-O- bonds, use of more precise models and inclusion of 1-3 interactions seems to be necessary.

NASA Program Exobiology↗
NASA NTRS2000

Effective Potential Energies and Transport Cross Sections for Interactions of Hydrogen and Nitrogen

The interaction energies for N2-He and N2-H2 are calculated by accurate ab initio methods. The virial coefficient and differential scattering cross section for N2-H2 are calculated; the theoretical results are compared with experimental data. The transport collision integrals for N2-H2 and N2-N2 interactions are calculated and tabulated; the results yield transport coefficients that compare well with measured data. Transport coefficients are found to be determined accurately from the interaction energies for a specific configuration of the molecule formed from the interaction partners. Comparisons with results of measurement and accurate calculations demonstrate that the transport properties of complex molecular interactions can be determined rapidly and fairly accurately from the interaction energies of simpler system using combination rules for the short-range parameters of effective interaction energies and the coefficients for the long-range forces. The coefficients for a two-parameter temperature expansion of diffusion and viscosity are tabulated for a realistic universal potential energy that is based primarily on the results of very accurate calculations of the He-He interaction energy.

Stallcop, James R.↗