Search NASA⌕ Search

SEARCH · Search NASA

Results for “Electron correlation calculations”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
NASA NTRS2023

Effect of the Electrostatic Field due to the Surface Monolayer Metal Atoms on the Dissociation of Homonuclear Diatomic Gases in Gas-Metal Surface Reactions

The present paper examines the role of an electrostatic field generated by the outermost monolayer of metal ions prior to gas adsorption in aiding the dissociation of homonuclear diatomic gas molecules. The interaction of five homonuclear diatomic gases, Cl 2 , F 2 , H 2 , N 2 and O 2 , with several pure metals are examined using Coulomb’s law to calculate the attractive and repulsive forces between the electrons or ions in the gas molecule and the free surface metallic electrons or ions assuming a Bohr model. These calculations demonstrate that the total energy of the electrostatic fields from the metals can exceed the molecular binding energies of Cl 2 , F 2 , and O 2 at some distance from the metallic surface thereby suggesting that these gases interact primarily with the metallic surface in their atomic states after molecular bond dissociation prior to reaction. In contrast, H 2 and N 2 gases do not dissociate prior to reaching the metal surface due to the fact that the effective charge of the gas ions is less than the total electron charge at the outermost electronic shell. The present results correlate linearly with the electrochemical series standard reduction potential as well as with the Pauling electronegativity for several metals.

Gas-metal reactions↗
NASA NTRS1995

The bright knots at the tops of soft X-ray flare loops: Quantitative results from Yohkoh

Soft X-ray Telescope (SXT) observations from the Japanese Yohkoh spacecraft have shown that confined bright regions are common features at the tops of flare loops throughout most of the duration of the flares. In this paper we present quantitative results for these flare knots, in relation to other flare regions, for four relatively 'simple' flares. Emission measure distributions, electron temperatures, and electron densities are derived from SXT and Yohkoh Bragg Crystal Spectrometer (BCS) observations. The four flares selected are dominated by what appear to be single-loop structures, with bright knots at the loop tops. The flares are neither long-duration nor impulsive events. The spatial distributions of brightness and emission measure in the flares are found to be quite similar for all four events, even though there are significant differences in dynamical behavior between at least two of the events. Temperatures and densities calculated for these flares are consistent with previous results from many solar experiments. An investigation of intensity correlations between adjacent pixels at the tops of the loops suggests the existence of local disturbances in the magnetic loops that occur on spatial scales less than the radii of the loops.

Doschek, G. A.↗
NASA NTRS1992

Connected triple excitations in coupled-cluster calculations of hyperpolarizabilities: Neon

We have calculated the second hyperpolarizability gamma of neon using the CCSD(T) method. The accuracy of the CCSD(T) approach has been established by explicit comparison with the single, double and triple excitation coupled-cluster (CCSDT) method using extended basis sets that are known to be adequate for the description of gamma. Our best estimate for gamma(sub 0) of 110 +/- 3 a.u. is in good agreement with other recent theoretical values and with Shelton's recent experimental estimate of 108 +/- 2 a.u. Comparison of the MP2 and CCSD(T) hyperpolarizability values indicates that MP2 gives a very good description of the electron correlation contribution to gamma(sub 0). We have combined MP2 frequency-dependent corrections with the CCSD(T) gamma(sub 0) to yield values of gamma(-2 omega;omega,omega,0) and gamma(exp K)(-omega;omega,0,0).

Rice, Julia E.↗
NASA NTRS2008

Symmetric Phase-Only Filtering in Particle-Image Velocimetry

Symmetrical phase-only filtering (SPOF) can be exploited to obtain substantial improvements in the results of data processing in particle-image velocimetry (PIV). In comparison with traditional PIV data processing, SPOF PIV data processing yields narrower and larger amplitude correlation peaks, thereby providing more-accurate velocity estimates. The higher signal-to-noise ratios associated with the higher amplitude correlation peaks afford greater robustness and reliability of processing. SPOF also affords superior performance in the presence of surface flare light and/or background light. SPOF algorithms can readily be incorporated into pre-existing algorithms used to process digitized image data in PIV, without significantly increasing processing times. A summary of PIV and traditional PIV data processing is prerequisite to a meaningful description of SPOF PIV processing. In PIV, a pulsed laser is used to illuminate a substantially planar region of a flowing fluid in which particles are entrained. An electronic camera records digital images of the particles at two instants of time. The components of velocity of the fluid in the illuminated plane can be obtained by determining the displacements of particles between the two illumination pulses. The objective in PIV data processing is to compute the particle displacements from the digital image data. In traditional PIV data processing, to which the present innovation applies, the two images are divided into a grid of subregions and the displacements determined from cross-correlations between the corresponding sub-regions in the first and second images. The cross-correlation process begins with the calculation of the Fourier transforms (or fast Fourier transforms) of the subregion portions of the images. The Fourier transforms from the corresponding subregions are multiplied, and this product is inverse Fourier transformed, yielding the cross-correlation intensity distribution. The average displacement of the particles across a subregion results in a displacement of the correlation peak from the center of the correlation plane. The velocity is then computed from the displacement of the correlation peak and the time between the recording of the two images. The process as described thus far is performed for all the subregions. The resulting set of velocities in grid cells amounts to a velocity vector map of the flow field recorded on the image plane. In traditional PIV processing, surface flare light and bright background light give rise to a large, broad correlation peak, at the center of the correlation plane, that can overwhelm the true particle- displacement correlation peak. This has made it necessary to resort to tedious image-masking and background-subtraction procedures to recover the relatively small amplitude particle-displacement correlation peak. SPOF is a variant of phase-only filtering (POF), which, in turn, is a variant of matched spatial filtering (MSF). In MSF, one projects a first image (denoted the input image) onto a second image (denoted the filter) as part of a computation to determine how much and what part of the filter is present in the input image. MSF is equivalent to cross-correlation. In POF, the frequency-domain content of the MSF filter is modified to produce a unitamplitude (phase-only) object. POF is implemented by normalizing the Fourier transform of the filter by its magnitude. The advantage of POFs is that they yield correlation peaks that are sharper and have higher signal-to-noise ratios than those obtained through traditional MSF. In the SPOF, these benefits of POF can be extended to PIV data processing. The SPOF yields even better performance than the POF approach, which is uniquely applicable to PIV type image data. In SPOF as now applied to PIV data processing, a subregion of the first image is treated as the input image and the corresponding subregion of the second image is treated as the filter. The Fourier transforms from both the firs and second- image subregions are normalized by the square roots of their respective magnitudes. This scheme yields optimal performance because the amounts of normalization applied to the spatial-frequency contents of the input and filter scenes are just enough to enhance their high-spatial-frequency contents while reducing their spurious low-spatial-frequency content. As a result, in SPOF PIV processing, particle-displacement correlation peaks can readily be detected above spurious background peaks, without need for masking or background subtraction.

Wemet, Mark P.↗
NASA NTRS1990

FT-IR spectroscopic studies of polycyclic aromatic hydrocarbons

Proper assessment of the hypothesis which correlates polycyclic aromatic hydrocarbons (PAHs) with the unidentified infrared emission bands requires additional experimental laboratory data. In order to address this need, thermal infrared emission studies were performed on a subset of PAHs suggested to be of astrophysical importance. It was proposed that infrared emission from interstellar PAHs occurs following absorption of an ultraviolet photon. Since energy transfer to the ground electronic state can be rapid for a species in which intersystem crossing is negligible, the emission spectrum may be viewed as resulting from an equilibrium vibrational temperature (Leger and d'Hendecourt, 1987). This has been the basis for using infrared absorption spectra to calculate the corresponding emission spectra at various temperatures. These calculations were made using room temperature infrared absorption coefficients instead of those at the temperature of interest because of the latter's unavailability. The present studies are designed to address the differences between the calculated and experimental thermal emission spectra and to provide information which will be useful in future ultraviolet induced infrared fluorescence studies. The emission spectra have been obtained for temperatures up to 825K using an emission cell designed to mount against an external port of an FT-IR spectrometer. These spectra provide information concerning relative band intensities and peak positions which is unavailable from previous calculations.

Salisbury, D. W.↗
NASA NTRS1988

Full configuration-interaction study of the ionic-neutral curve crossing in LiF

Full configuration-interaction (FCI) calculations are used to assess the relative ability of methods for truncating the n-particle expansion in describing the ionic-neutral curve crossing between the two lowest Sigma(+) states of LiF. While the FCI calculations yield a smooth dipole moment function, MRCI calculations based on CASSCF orbitals optimized for the lowest state at all r values yield a discontinuous dipole moment function. However, when the orbitals are optimized using a state-averaged CASSCF procedure, with equal weights for the ionic and neutral solutions, both the CASSCF and MRCI dipole moment functions are smooth and in reasonable agreement with the FCI. No single-reference-based method is found to work satisfactorily. Potential curves for the lowest two Sigma(+) states are determined in both the adiabatic and diabatic representations using a large atomic natural orbit Gaussian basis set and a state-averaged CASSCF/MRCI treatment of electron correlation.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1987

Surface characterization in composite and titanium bonding: Carbon fiber surface treatments for improved adhesion to thermoplastic polymers

The effect of anodization in NaOH, H2SO4, and amine salts on the surface chemistry of carbon fibers was examined by X-ray photoelectron spectroscopy (XPS). The surfaces of carbon fibers after anodization in NaOH and H2SO4 were examined by scanning transmission electron microscopy (STEM), angular dependent XPS, UV absorption spectroscopy of the anodization bath, secondary ion mass spectrometry, and polar/dispersive surface energy analysis. Hercules AS-4, Dexter Hysol XAS, and Union Carbide T-300 fibers were examined by STEM, angular dependent XPS, and breaking strength measurement before and after commercial surface treatment. Oxygen and nitrogen were added to the fiber surfaces by anodization in amine salts. Analysis of the plasmon peak in the carbon 1s signal indicated that H2SO4 anodization affected the morphological structure of the carbon fiber surface. The work of adhesion of carbon fibers to thermoplastic resins was calculated using the geometric mean relationship. A correlation was observed between the dispersive component of the work of adhesion and the interfacial adhesion.

Devilbiss, T. A.↗
NASA NTRS2007

Theoretical Studies of Routes to Synthesis of Tetrahedral N4

A paper [Chem. Phys. Lett. 345, 295 (2001)] describes theoretical studies of excited electronic states of nitrogen molecules, with a view toward utilizing those states in synthesizing tetrahedral N4, or Td N4 a metastable substance under consideration as a high-energy-density rocket fuel. Several ab initio theoretical approaches were followed in these studies, including complete active space self-consistent field (CASSCF), state-averaged CASSCF (SA-CASSCF), singles configuration interaction (CIS), CIS with second-order and third-order correlation corrections [CIS(D) and CIS(3)], and linear response singles and doubles coupled-cluster (LRCCSD). Standard double zeta polarized and triple zeta double polarized one-particle basis sets were used. The CASSCF calculations overestimated the excitation energies, while SACASSCF calculations partly corrected these overestimates. The accuracy of the CIS calculations varied, depending on the particular state, while the CIS(D), CIS(3), and LRCCSD results were in generally good agreement. The energies of the lowest six excited singlet states of Td N4 as calculated by the LRCCSD were compared with the energies of possible excited states of N2 + N2 fragments, leading to the conclusion that the most likely route for synthesis of Td N4 would involve a combination of two bound quintet states of N2.

Lee, Timothy J.↗
NASA NTRS1983

On the nature of the bonding in Cu2 - An ab initio viewpoint

The bonding in Cu2 has been calculatively investigated. A CASSCF calculation is performed where the two 4s electrons are distributed in all possible ways among the 4s and 4p orbitals. The CAS results have a 3d population of 9.99. The corresponding orbitals between the CAS core orbitals at r(e) and the atomic SCF core orbitals show an overlap of 13.9992 out of a possible 14, with all of the change in sigma space. Thus, the CAS results show virtually no change in the d orbitals relative to the atom and can be considered as showing only a single bond. The reduction in 3d population, the decrease in r(e), and the increase in D(e) upon correlating the 3d shell indicates that the 3d electrons are slightly involved in the bonding, but there is no indication of the formation of a triple bond.

Bauschlicher, C. W., Jr.↗
NASA NTRS2007

Liquid Bismuth Propellant Flow Sensor

Quantifying the propellant mass flow rate in liquid bismuth-fed electric propulsion systems has two challenging facets. First, the flow sensors must be capable of providing a resolvable measurement at propellant mass flow rates on the order of 10 mg/see with and uncertainty of less that 5%. The second challenge has to do with the fact that the materials from which the flow sensors are fabricated must be capable of resisting any of the corrosive effects associated with the high-temperature propellant. The measurement itself is necessary in order to properly assess the performance (thrust efficiency, Isp) of thruster systems in the laboratory environment. The hotspot sensor[I] has been designed to provide the bismuth propellant mass flow rate measurement. In the hotspot sensor, a pulse of thermal energy (derived from a current pulse and associated joule heating) is applied near the inlet of the sensor. The flow is "tagged" with a thermal feature that is convected downstream by the flowing liquid metal. Downstream, a temperature measurement is performed to detect a "ripple" in the local temperature associated with the passing "hotspot" in the propellant. By measuring the time between the upstream generation and downstream detection of the thermal feature, the flow speed can be calculated using a "time of flight" analysis. In addition, the system can be calibrated by measuring the accumulated mass exiting the system as a-function of time and correlating this with the time it takes the hotspot to convect through the sensor. The primary advantage of this technique is that it doesn't depend on an absolute measurement of temperature but, instead, relies on the observation of thermal features. This makes the technique insensitive to other externally generated thermal fluctuations. In this paper, we describe experiments performed using the hotspot flow sensor aimed at quantifying the resolution of the sensor technology. Propellant is expelled onto an electronic scale to provide an independent measure of the propellant mass flow rate as a function of time. In addition, two separate detection schemes are employed. The first uses a thermocouple to directly measure temperature in the fluid. The second involves the ,use of a fiber optic coupled to a photodiode allowing for detection of an increase in light emission from the fluid as the hotspot passes. the detection location.

Polzin, Kurt A.↗
NASA NTRS2007

Nonthermal X-ray Spectral Flattening toward Low Energies in Early Impulsive Flares

The determination of the low-energy cutoff to nonthermal electron distributions is critical to the calculation of the nonthermal energy in solar flares. The most direct evidence for low-energy cutoffs is flattening of the power-law, nontherma1 X-ray spectra at low energies. However, because of the plasma preheating often seen in flares, the thermal emissions at low energies may hide such spectral flattening of the nonthermal component. We select a category of flares, which we call "early impulsive flares", in which the > 25 keV hard X-ray (HXR) flux increase is delayed by less than 30 s after the flux increase at lower energies. Thus, the plasma preheating in these flares is minimal, so the nonthermal spectrum can be determined to lower energies than in flares with significant preheating. Out of a sample of 33 early impulsive flares observed by the Ramaty High Energy Solar Spectroscopy Imager (RHESSI), 9 showed spectral flattening toward low energies. In these events, the break energy of the double power-law fit to the HXR spectra lies in the range of 10-50 keV, significantly lower than the value we have seen for other flares that do not show such early impulsive emissions. In particular, it correlates with the HXR flux. After correcting the spatially-integrated spectra for albedo from isotropically emitted X-rays and using RHESSI imaging spectroscopy to exclude the extended albedo halo, we find that albedo associated with isotropic or nearly isotropic electrons can only account for the spectral flattening in 3 flares near Sun center. The spectral flattening in the remaining 6 flares is found to be consistent with the existence of a low-energy cutoff in the electron spectrum, falling in the range of 15-50 keV, which also correlates with the HXR flux.

Holman, Gordon D.↗
NASA NTRS1992

Crab pulsar giant pulses: Simultaneous radio and GRO observations

Observations are reported of the Crab pulsar made at radio frequencies concurrent with Oriented Scintillation Spectrometer Experiment (OSSE) observations from 15 to 27 May 1991. Using the 43 m telescope at Green Bank at 0.8 and 1.4 GHz, samples were made continuously for 10 hrs/day at intervals of 100 to 300 microsecs. The analysis of the radio data includes calculation of histograms of pulse intensities, absolute timing to about 20 microsec precision, and characterization of intensity variations on time scales from the 33 ms spin period to days. The most detailed analysis is presented made of giant pulses. The ultimate goal is to bin the radio data into giant and nongiant pulses and to form average waveforms of OSSE data for the corresponding pulse periods. A test is done to see whether the violet radio fluctuations (which are not seen in other radio pulsars to the same degree) are correlated with low energy gamma rays, yielding constraints on the radio coherence mechanism and the steadiness of the electron-positron outflow in the magnetosphere. Timing analysis of the radio data provides a well defined ephemeris over the specified range of epochs. The gamma ray pulse phase was predicted with an error of less than 70 microsecs.

Lundgren, Scott C.↗
NASA NTRS1992

Observations of the structure and vertical transport of the polar upper ionosphere with the EISCAT VHF radar. II - First investigations of the topside O(+) and H(+) vertical ion flows

EISCAT VHF radar was used to investigate the vertical flows of H(+) and O(+) ions in the topside high-latitude ionosphere. The radar transmitted a single long pulse to probe the ionosphere from 300 to 1200 km altitude. A calculation scheme is developed to deduce the H(+) drift velocity from the coupled momentum equations of H(+), O(+), and the electrons, using the radar data and a neutral atmosphere model. The H(+) vertical drift velocity was expressed as a linear combination of the different forces acting on the plasma. Two nights, one very quiet, one with moderate magnetic activity, were used to test the technique and to provide a first study of the morphology and orders of magnitudes of ion outflow fluxes over Tromso. O(+) vertical flows were found to be downward or close to zero most of the time in the topside ionosphere; they appeared to be strongly correlated with magnetic activity during the disturbed night. H(+) topside ion fluxes were always directed upward, with velocity reaching 500-1000 m/s. A permanent outflow of H(+) ions is inferred.

Wu, Jian↗
NASA NTRS1987

A simple interpretation of the Fe2(-) photoelectron spectrum

The photoelectron spectrum of Fe2(-) can be simply interpreted in terms of electron detachment from the mildly bonding 4s sigma sup * sub u orbital of a (4s sigma sub s)(sup 2) (4s sigma sup * sub u)(sup 2) (3d)(sup 13) anion. This interpretation implies a (4s sigma sub g)(sup 2) (4s sigma sup * sub u)(sup1) (3d)(sup13) configuration for the ground state of Fe2, correlating with one ground state (4s2 3d6) and one excited state (4s1 3d7) Fe atom. A comparison of the bond length and vibrational frequency of Fe2 to values for transition metal dimers containing single 4s-4s bonds is suggestive of 3d-3d bonding in this molecule. The results of preliminary full-valence configuration interaction calculations provide stron support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
NASA NTRS2019

Highly Accurate Quartic Force Field and Rovibrational Spectroscopic Constants for the Azirinyl Cation (c-C2NH2+) and Its Isomers

Azirinyl cation is an aromatic cyclic molecule that is isoelectronic with cyclopropenylidene, c-C3H2, and c-C3H3+. Cyclopropenylidene has been shown to be ubiquitous, existing in many different astrophysical environments. Given the similar chemistry between C and N, and the relative abundances between C and N in astrophysical environments, it is expected that there should be aromatic ringed molecules that incorporate N in the ring, but as yet, no such molecule has been identified. To address this issue, the present study uses high levels of electronic structure theory to compute a highly accurate quartic force field (QFF) for azirinyl cation and its two lowest lying isomers, the cyanomethyl and isocyanomethyl cations. The theoretical approach uses the singles and doubles coupled-cluster method that includes a perturbative correction for connected triple excitations, CCSD(T), together with extrapolation to the one-particle basis set limit and corrections for scalar relativity and core-correlation. The QFF is then used in a second order vibrational perturbation theory analysis (VPT2) to compute the fundamental vibrational frequencies and rovibrational spectroscopic constants for all three C2NH2+ isomers. The reliability of the VPT2 vibrational frequencies is tested by comparison to vibrational configuration interaction (VCI) calculations and excellent agreement is found between the two approaches. Fundamental vibrational frequencies and rovibrational spectroscopic constants for all singly substituted 13C, 15N, and D isotopologues are also reported. It is expected that the highly accurate spectroscopic data reported herein will be useful in the identification of these cations in high resolution experimental or astronomical observations.

Partha P Bera↗
NASA NTRS1989

Relativistic magnetospheric electrons: Lower ionospheric conductivity and long-term atmospheric variability

Long term observations of relativistic electrons in the earth's outer magnetosphere show a strong solar cycle dependence with a prominent intensity maximum during the approach to solar minimum. This population therefore closely corresponds to the presence of high speed solar wind streams emanating from solar coronal holes. Using a numerical code, the precipitating electron energy deposition in the earth's upper and middle atmosphere were calculated. Observed events (typically persisting several days) would have maximum effect in the 40 to 60 km altitude range with peak energy depositions greater than 110 keV/cu cm-s. It is suggested that this electron population could play an important long term role in modulating lower D region ionization and middle atmospheric ozone chemistry. Methods are described of observing middle atmospheric and lower ionospheric effects of the electrons including balloon, riometer, and space-based ozone sensor systems. A particularly promising approach may involve the monitoring of global Schumann resonance modes which are sensitive to global changes in the properties of the earth-ionosphere cavity. Present work indicates that Schumann resonance properties are moderately correlated with the flux of precipitating relativistic electrons thus offering the possibility of continuously monitoring this aspect of magnetosphere-atmosphere coupling.

Baker, D. N.↗
NASA NTRS1994

Equilibrium and Dynamics Properties of Poly(oxyethylene) Melts and Related Poly(alkylethers) from Simulations and Ab Initio Calculations

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.

Smith, Grant D.↗
NASA NTRS1989

Theoretical study of metal noble-gas positive ions

Theoretical calculations have been performed to determine the spectroscopic constant for the ground and selected low-lying electronic states of the transition-metal noble-gas ions Var(+), FeAr(+), CoAr(+), CuHe(+), CuAr(+), and CuKr(+). Analogous calculations have been performed for the ground states of the alkali noble-gas ions LiAr(+), LiKr(+), NaAr(+), and KAr(+) and the alkaline-earth noble-gas ion MgAr(+) to contrast the difference in binding energies between the simple and transition-metal noble-gas ions. The binding energies increase with increasing polarizability of the noble-gas ions, as expected for a charge-induced dipole bonding mechanism. It is found that the spectroscopic constants of the X 1Sigma(+) states of the alkali noble-gas ions are well described at the self-consistent field level. In contrast, the binding energies of the transition-metal noble-gas ions are substantially increased by electron correlation.

Bauschlicher, Charles W., Jr.↗