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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1982

Prediction of molecular infrared band and line intensities

The general problem of predicting infrared intensities is examined. The problem of predicting line intensities is discussed with attention focussed specifically on the problem of predicting vibrational strengths (or total band intensities). Two methods are considered: predictions based on ab initio quantum mechanical calculations, and predictions based on the transfer of atomic polar tensor parameters from small model molecules to the molecule of interest. Comparisons of predicted spectra with experimental spectra are shown for CH3OH, CH3OCH3, C2H5OH, and HOC2. It is suggested that the most important application of this work may be to the prediction of intensities for free radicals, ions, and reactive intermediates so that the infrared spectrum can be used in the quantitative analysis for these interesting species.

Person, W. B.↗
NASA NTRS1984

Metastability of isoformyl ions in collisions with helium and hydrogen

The stability of HOC(+) ions under conditions in interstellar molecular clouds is considered. In particular, the possibility that collisions with helium or hydrogen will induce isomerization to the stable HCO(+) form is examined theoretically. Portions of the electronic potential energy surfaces for interaction with He and H atoms are obtained from standard quantum mechanical calculations. Collisions with He atoms are found to be totally ineffective for inducing isomerization. Collisions with H atoms are found to be ineffective at low interstellar temperatures owing to a small (about 500 K) barrier in the entrance channel; at higher temperatures where this barrier can be overcome, however, collisions with hydrogen atoms do result in conversion to the stable HCO(+) form. Although detailed calculations are not presented, it is argued that low-energy collisions with H2 molecules are also ineffective in destroying the metastable ion.

Green, S.↗
NASA NTRS1987

Design considerations for a GaAs nipi doping superlattice solar cell

A new GaAs nipi doping superlattice solar cell structure is presented, which holds promise for high efficiency coupled with very high radiation tolerance. The structure has all contacts on the unilluminated side. Design constraints are presented which this structure must satisfy in order to exhibit high efficiency and high radiation tolerance. The results of self-consistent quantum mechanical calculations are presented which show that a viable design of this cell would include relatively thick n and p layers which are fairly heavily doped.

Clark, Ralph↗
NASA NTRS1988

Effect of orbital and rotational angular momentum averaging on branching ratios of dynamical resonances in the reaction H + p-H2 yields o-H2 + H

The paper reports extensive quantum mechanical calculations of the product vibrational branching ratios in the reaction H + p-H2 yields o-H2 + H. The calculations involve total angular momentum up to 2 and excited as well as ground initial rotational states, and they are completely converged with up to 513 channels in individual total angular momentum/parity blocks. Comparisons are made with recent experiments by Nieh and Valentini.

Mladenovic, Mirjana↗
NASA NTRS1989

Spectroscopic analysis of transition state energy levels - Bending-rotational spectrum and lifetime analysis of H3 quasibound states

Converged quantum mechanical calculations of scattering matrices and transition probabilities are reported for the reaction of H with H2 with total angular momentum 0, 1, and 4 as functions of total energy in the range 0.85-1.15 eV on an accurate potential energy surface. The resonance structure is illustrated with Argand diagrams. State-to-state reactive collision delay times and lifetimes are presented. For J = 0, 1, and 4, the lowest-energy H3 resonance is at total energies of 0.983, 0.985, and 1.01 eV, respectively, with lifetimes of about 16-17 fs. For J = 1 and 4 there is a higher-energy resonance at 1.10-1.11 eV. For J = 1 the lifetime is about 4 fs and for J = 4 it is about 1 fs.

Zhao, Meishan↗
NASA NTRS1990

Ultrahigh-pressure melting of lead - A multidisciplinary study

Measurements of the melting temperatures of lead, carried out to pressures of 1 megabar and temperatures near 4000 kelvin by means of a laser-heated diamond cell are in excellent agreement with the results of previous shock-wave experiments. The data are analyzed by means of first principles quantum mechanical calculations, and the agreement documents the reliability of current experimental and theoretical techniques for studies of melting at ultrahigh pressures. These studies have potentially wide-ranging applications from planetary science to condensed matter physics.

Godwal, B. K.↗
NASA NTRS1992

Ab initio atomic recombination reaction energetics on model heat shield surfaces

Ab initio quantum mechanical calculations on small hydration complexes involving the nitrate anion are reported. The self-consistent field method with accurate basis sets has been applied to compute completely optimized equilibrium geometries, vibrational frequencies, thermochemical parameters, and stable site labilities of complexes involving 1, 2, and 3 waters. The most stable geometries in the first hydration shell involve in-plane waters bridging pairs of nitrate oxygens with two equal and bent hydrogen bonds. A second extremely labile local minimum involves out-of-plane waters with a single hydrogen bond and lies about 2 kcal/mol higher. The potential in the region of the second minimum is extremely flat and qualitatively sensitive to changes in the basis set; it does not correspond to a true equilibrium structure.

Senese, Fredrick↗
NASA NTRS1999

Recent Development on O(+)-O Collision Frequency and Ionosphere-Middle Atmosphere Coupling

The collision frequency between an oxygen atom and its singly charged ion controls the transfer of energy between the solar radiation and the thermosphere. There were a long standing discrepancy, extending over a decade, between the theoretical and empirical determination of this frequency, and the empirical value of this frequency exceeded the theoretical value by a factor of 1.7. Recent improvements in theory were obtained by using accurate oxygen ion-oxygen atom potential energy curves, and partial wave quantum mechanical calculations. Similarly, recently three independent statistical methods were applied to the empirical determination of this frequency. These methods give results consistent with each other, and together with the recent theoretical improvements, bring the ratio close to unity, as it should be. It will be shown that the old statistical method for this determination contained accumulative errors, leading to a larger value for this ratio. The recent improvements lead to an average value of the empirical to the theoretical ratio equal to 0.98, with an uncertainty of +/- 8%, resolving the old discrepancy between theory and observations. The main source of uncertainties are errors in the profile of the oxygen atom density, which is of the order of 11 %. An alternative method to find the oxygen atom density is being suggested.

Omidvar, K.↗
NASA NTRS1999

Recent Development on O(+) - O Collision Frequency and Ionosphere-Thermosphere Coupling

The collision frequency between an oxygen atom and its singly charged ion controls the momentum transfer between the ionosphere and the thermosphere. There has been a long standing discrepancy, extending over a decade, between the theoretical and empirical determination of this frequency: the empirical value of this frequency exceeded the theoretical value by a factor of 1.7. Recent improvements in theory were obtained by using accurate oxygen ion-oxygen atom potential energy curves, and partial wave quantum mechanical calculations. We now have applied three independent statistical methods to the observational data, obtained at the MIT/Millstone Hill Observatory, consisting of two sets A and B. These methods give results consistent with each other, and together with the recent theoretical improvements, bring the ratio close to unity, as it should be. The three statistical methods lead to an average for the ratio of the empirical to the theoretical values equal to 0.98, with an uncertainty of +/-8%, resolving the old discrepancy between theory and observation. The Hines statistics, and the lognormal distribution statistics, both give lower and upper bounds for the Set A equal to 0.89 and 1.02, respectively. The related bounds for the Set B are 1.06 and 1.17. The average values of these bounds thus bracket the ideal value of the ratio which should be equal to unity. The main source of uncertainties are errors in the profile of the oxygen atom density, which is of the order of 11%. An alternative method to find the oxygen atom density is being suggested.

Omidvar, K.↗
NASA NTRS1999

Trace Chemistry

The goals of the trace chemistry group were to identify the processes relevant to aerosol and aerosol precursor formation occurring within aircraft gas turbine engines; that is, within the combustor, turbine, and nozzle. The topics of discussion focused on whether the chemistry of aerosol formation is homogeneous or heterogeneous; what species are important for aerosol and aerosol precursor formation; what modeling/theoretical activities to pursue; what experiments to carry out that both support modeling activities and elucidate fundamental processes; and the role of particulates in aerosol and aerosol precursor formation. The consensus of the group was that attention should be focused on SO2, SO3, and aerosols. Of immediate concern is the measurement of the concentration of the species SO3, SO2, H2SO4 OH, HO2, H2O2, O, NO, NO2, HONO, HNO3, CO, and CO2 and particulates in various engines, both those currently in use and those in development. The recommendation was that concentration measurements should be made at both the combustor exit and the engine exit. At each location the above species were classified into one of four categories of decreasing importance, Priority I through IV, as follows: Combustor exit: Priority I species - SO3:SO2 ratio, SO3, SO2, and particulates; Priority II species: OH and O; Priority III species - NO and NO2; and Priority IV species - CO and CO2. For the Engine exit: Priority I species - SO3:SO2 ratio, SO3, SO2,H2SO4, and particulates; Priority II species: OH,HO2, H2O2, and O; Priority III species - NO, NO2, HONO, and HNO3; and Priority IV species - CO and CO2. Table I summarizes the anticipated concentration range of each of these species. For particulate matter, the quantities of interest are the number density, size distribution, and composition. In order to provide data for validating multidimensional reacting flow models, it would be desirable to make 2-D, time-resolved measurements of the concentrations of the above species and, in addition, of the pressure, temperature, and velocity. A near term goal of the experimental program should be to confirm the nonlinear effects of sulfur speciation, and if present, to provide an explanation for them. It is also desirable to examine if the particulate matter retains any sulfur. The recommendation is to examine the effects on SOx production of variations in fuel-bound sulfur and aromatic content (which may affect the amount of particulates formed). These experiments should help us to understand if there is a coupling between particulate formation and SO, concentration. Similarly, any coupling with NOx can be examined either by introducing NOx into the combustion air or by using fuel-bound nitrogen. Also of immediate urgency is the need to establish and validate a detailed mechanism for sulfur oxidation/aerosol formation, whose chemistry is concluded to be homogeneous, because there is not enough surface area for heterogeneous effects. It is envisaged that this work will involve both experimental and theoretical programs. The experimental work will require, in addition to the measurements described above, fundamental studies in devices such as flow reactors and shock tubes. Complementing this effort should be modeling and theoretical activities. One impediment to the successful modeling of sulfur oxidation is the lack of reliable data for thermodynamic and transport properties for several species, such as aqueous nitric acid, sulfur oxides, and sulfuric acid. Quantum mechanical calculations are recommended as a convenient means of deriving values for these properties. Such calculations would also help establish rate constants for several important reactions for which experimental measurements are inherently fraught with uncertainty. Efforts to implement sufficiently detailed chemistry into computational fluid dynamic codes should be continued. Zero- and one-dimensional flow models are also useful vehicles for elucidating the minimal set of species and reactions that must be included in two- and three-dimensional modeling studies.

Radhakrishnan, Krishnan↗
NASA NTRS2001

Determination of the Hyperfine Structure of N2D(+)

We present new high spectral resolution observations of the N2D+ J = 2 yields 1 and J = 3 yields 2 as well as N2H+ J = 3 yields 2 lines, towards dense molecular cores. The hyperfine structure of the N2H+ and N2D+ transitions is clearly resolved in these sources, in excellent agreement with quantum mechanical calculations. Optical depths are determined from the observed spectra, leading to D/H values of the order of 10 - 30% for the N2D+/N2H+ system. There are a large number of hyperfine components and in addition to providing satellites they contribute to the broadening and asymmetric shapes of the N2H+ and N2D+ line profiles. It is therefore important to take into account the detailed hyperfine structure of the transitions when deducing astrophysical parameters from observed data.

Gerin, Maryvonne↗
NASA NTRS2001

Carbon Nanotubes in Water: MD Simulations of Internal and External Flow, Self Organization

We have developed computational tools, based on particle codes, for molecular dynamics (MD) simulation of carbon nanotubes (CNT) in aqueous environments. The interaction of CNTs with water is envisioned as a prototype for the design of engineering nano-devices, such as artificial sterocillia and molecular biosensors. Large scale simulations involving thousands of water molecules are possible due to our efficient parallel MD code that takes long range electrostatic interactions into account. Since CNTs can be considered as rolled up sheets of graphite, we expect the CNT-water interaction to be similar to the interaction of graphite with water. However, there are fundamental differences between considering graphite and CNTs, since the curvature of CNTs affects their chemical activity and also since capillary effects play an important role for both dynamic and static behaviour of materials inside CNTs. In recent studies Gordillo and Marti described the hydrogen bond structure as well as time dependent properties of water confined in CNTs. We are presenting results from the development of force fields describing the interaction of CNTs and water based on ab-initio quantum mechanical calculations. Furthermore, our results include both water flows external to CNTs and the behaviour of water nanodroplets inside heated CNTs. In the first case (external flows) the hydrophobic behaviour of CNTs is quantified and we analyze structural properties of water in the vicinity of CNTs with diagnostics such as hydrogen bond distribution, water dipole orientation and radial distribution functions. The presence of water leads to attractive forces between CNTs as a result of their hydrophobicity. Through extensive simulations we quantify these attractive forces in terms of the number and separation of the CNT. Results of our simulations involving arrays of CNTs indicate that these exhibit a hydrophobic behaviour that leads to self-organising structures capable of trapping water clusters. In the second case (internal flows) we study the behaviour of water droplets confined inside CNTs. Constant temperature simulations allow us to capture structural properties such as the contact angles and density profiles of the equilibrated drops. By heating and subsequently cooling of the CNT, we are able to measure the evaporation and the condensation rate of the entrapped water.

Jaffe, Richard L.↗
NASA NTRS2003

Scalability of a Low-Cost Multi-Teraflop Linux Cluster for High-End Classical Atomistic and Quantum Mechanical Simulations

Scalability of a low-cost, Intel Xeon-based, multi-Teraflop Linux cluster is tested for two high-end scientific applications: Classical atomistic simulation based on the molecular dynamics method and quantum mechanical calculation based on the density functional theory. These scalable parallel applications use space-time multiresolution algorithms and feature computational-space decomposition, wavelet-based adaptive load balancing, and spacefilling-curve-based data compression for scalable I/O. Comparative performance tests are performed on a 1,024-processor Linux cluster and a conventional higher-end parallel supercomputer, 1,184-processor IBM SP4. The results show that the performance of the Linux cluster is comparable to that of the SP4. We also study various effects, such as the sharing of memory and L2 cache among processors, on the performance.

Kikuchi, Hideaki↗
NASA NTRS2004

Ceramic Interconnects with Low Sintering Temperature

Ceramic interconnects for use in solid oxide he1 cells are expected to operate between 900 to approximately 1000 C, sinter below 1400 C to allow co-firing and meet a number thermal mechanical requirements. The pervoskite type (ABO3) lanthanum chromite based materials have emerged as a leading candidate that will meet these criteria by varying the composition on the A and B sites. A need therefore exists to determine this material's temperature dependent electrical and mechanical properties with respect to these site substitutions. In this investigation oxide powders were prepared by the glycine-nitrate process. Ionic substitutions were carried out on A sites with Ca or Sr, and B sites with Co and Al, respectively. Only stoichiometric compositions were considered for the sake of stability. The powders and their ability to sinter were investigated by XRD, SEM, dilatometry and density measurements. The sintered materials were further examined by SEM, thermal expansion and electric conductivity measurements in order to elucidate the resulting microstructure, electrical and mechanical properties. In addition quantum mechanical calculations were performed to obtain insight into the effects of these dopants on the materials electronic band structure and lattice parameter.

Zhong, Zhi-Min↗
NASA NTRS2008

Special Polymer/Carbon Composite Films for Detecting SO2

A family of polymer/carbon films has been developed for use as sensory films in electronic noses for detecting SO2 gas at concentrations as low as 1 part per million (ppm). Most previously reported SO2 sensors cannot detect SO2 at concentrations below tens of ppm; only a few can detect SO2 at 1 ppm. Most of the sensory materials used in those sensors (especially inorganic ones that include solid oxide electrolytes, metal oxides, and cadmium sulfide) must be used under relatively harsh conditions that include operation and regeneration at temperatures greater than 100 C. In contrast, the present films can be used to detect 1 ppm of SO2 at typical opening temperatures between 28 and 32 C and can be regenerated at temperatures between 36 and 40 C. The basic concept of making sensing films from polymer/carbon composites is not new. The novelty of the present family of polymer/carbon composites lies in formulating the polymer components of these composites specifically to optimize their properties for detecting SO2. First-principles quantum-mechanical calculations of the energies of binding of SO2 molecules to various polymer functionalities are used as a guide for selecting polymers and understanding the role of polymer functionalities in sensing. The polymer used in the polymer-carbon composite is a copolymer of styrene derivative units with vinyl pyridine or substituted vinyl pyridine derivative units. To make a substituted vinyl pyridine for use in synthesizing such a polymer, poly(2-vinyl pyridine) that has been dissolved in methanol is reacted with 3-chloropropylamine that has been dissolved in a solution of methanol. The methanol is then removed to obtain the copolymer. Later, the copolymer can be dissolved in an appropriate solvent with a suspension of carbon black to obtain a mixture that can be cast and then dried to obtain a sensory film.

Homer, Margie↗
NASA NTRS2012

Kuang's Semi-Classical Formalism for Electron Capture Cross-Sections in Ion-Ion Collisions at Approximately to MeV/amu: Application to ENA Modeling

Recent discovery by STEREO A/B of energetic neutral hydrogen is spurring an interest and need for reliable estimates of electron capture cross sections at few MeVs per nucleon as well as for multi-electron ions. Required accuracy in such estimates necessitates detailed and involved quantum-mechanical calculations or expensive numerical simulations. For ENA modeling and similar purposes, a semi-classical approach offers a middle-ground approach. Kuang's semiclassical formalism to calculate electron-capture cross sections for single and multi-electron ions is an elegant and efficient method, but has so far been applied to limited and specific laboratory measurements and at somewhat lower energies. Our goals are to test and extend Kuang s method to all ion-atom and ion-ion collisions relevant to ENA modeling, including multi-electron ions and for K-shell to K-shell transitions.

Barghouty, A. F.↗
NASA NTRS1960

Energies of Various Interactions Between Hydrogen and Helium Atoms and Ions

A compilation is made of those interactions between hydrogen and helium atoms and ions whose potential curves are well established by virtue of being based on experimental data or on essentially exact quantum-mechanical calculations. These potential curves have been fitted with well-known empirical forms which should be useful in calculations of transport properties involving these interactions.

Fallon, Robert J.↗
DOE OSTI2022

Chemical Kinetics Underlying the Sooting Tendency and Auto-Ignition Characteristics of Linear, Branched, and Cyclic Ether Compounds

Biofuels present opportunities for improving the performance and reducing emissions from internal combustion engines by incorporating oxygenated functional groups to the fuels. Among various oxygenates, ethers have been recognized as promising candidates for an alternative to conventional diesel fuel owing to their higher reactivity and lower sooting tendency. The detailed guidelines for designing ethers, however, have not been fully discussed, even though their combustion characteristics are sensitive to the molecular structure. This study was devoted to exploring the structure-property relationships, particularly focusing on the cetane number and yield sooting index, using five linear, branched, and cyclic ethers: di-amyl-ether, 4-butoxy-heptane, 3,3-dimethyl-oxetane, 2-ethyl-4-methyl-1,3-dioxolane, and 2-isopropyl-4-methyl-1,3-dioxolane. First, we examined the chemical kinetics underlying the sooting tendency of the test fuels. The combustion product distribution was measured from flow reactor experiments at 750-1100 K, F=3, at atmospheric pressure. As a result, it was revealed that the sooting tendency is closely related to the size of hydrocarbon intermediates in the high-temperature regime (>1000 K); that is, larger hydrocarbons lead to more soot precursor formation. The underlying chemistry determining the size of the hydrocarbons from the tested fuels was analyzed using reaction pathway analysis and quantum mechanics calculations, which showed that the branched and cyclic ether structures form abundant C3-C4 compounds. Moreover, the auto-ignition characteristics of the test fuels were studied using the flow reactor at low-temperature (400-700 K) and F=1. We found a clear difference in the combustion-product distribution from high and low reactivity fuels, which was then correlated to the systematic analysis of the key reaction energy barriers with the varying molecular structure.

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND AN↗