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At least 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

The Anharmonic Force Field of Ethylene, C2H4, by Means of Accurate Ab Initio Calculations

The quartic force field of ethylene, C2H4, has been calculated ab initio using augmented coupled cluster, CCSD(T), methods and correlation consistent basis sets of spdf quality. For the C-12 isotopomers C2H4, C2H3D, H2CCD2, cis-C2H2D2, trans-C2H2D2, C2HD3, and C2D4, all fundamentals could be reproduced to better than 10 per centimeter, except for three cases of severe Fermi type 1 resonance. The problem with these three bands is identified as a systematic overestimate of the Kiij Fermi resonance constants by a factor of two or more; if this is corrected for, the predicted fundamentals come into excellent agreement with experiment. No such systematic overestimate is seen for Fermi type 2 resonances. Our computed harmonic frequencies suggest a thorough revision of the accepted experimentally derived values. Our computed and empirically corrected re geometry differs substantially from experimentally derived values: both the predicted rz geometry and the ground-state rotational constants are, however, in excellent agreement with experiment, suggesting revision of the older values. Anharmonicity constants agree well with experiment for stretches, but differ substantially for stretch-bend interaction constants, due to equality constraints in the experimental analysis that do not hold. Improved criteria for detecting Fermi and Coriolis resonances are proposed and found to work well, contrary to the established method based on harmonic frequency differences that fails to detect several important resonances for C2H4 and its isotopomers. Surprisingly good results are obtained with a small spd basis at the CCSD(T) level. The well-documented strong basis set effect on the v8 out-of-plane motion is present to a much lesser extent when correlation-optimized polarization functions are used. Complete sets of anharmonic, rovibrational coupling, and centrifugal distortion constants for the isotopomers are available as supplementary material to the paper.

Martin, Jan M. L.↗
NASA NTRS1996

Wavelet-Based Grid Generation

Wavelets can provide a basis set in which the basis functions are constructed by dilating and translating a fixed function known as the mother wavelet. The mother wavelet can be seen as a high pass filter in the frequency domain. The process of dilating and expanding this high-pass filter can be seen as altering the frequency range that is 'passed' or detected. The process of translation moves this high-pass filter throughout the domain, thereby providing a mechanism to detect the frequencies or scales of information at every location. This is exactly the type of information that is needed for effective grid generation. This paper provides motivation to use wavelets for grid generation in addition to providing the final product: source code for wavelet-based grid generation.

HIGH PASS FILTERS↗
NASA NTRS1991

The structure and energetics of the HCN-HNC transition state

The optimum geometries and quadratic force constants of HCN, HNC and the transition state connecting them have been determined at the single- and double-excitation coupled-cluster (CCSD) and CCSD(T) levels of theory. Energy differences were evaluated using the CCSD and CCSD(T) methods in conjunction with large atomic natural orbital basis sets containing g-type basis functions on the heavy atoms and f-type functions on hydrogen. The most reliable structure obtained for the transition state has bond distances of 1.194, 1.188, and 1.389 A for r(CN), r(CH), and r(NH), respectively. Including a correction for zero-point vibrational energies, the transition state is predicted to be 44.6 + or - 1.0 kcal/mol above the HCN isomer, while HNC is predicted to be 14.4 + or - 1.0 kcal/mol above HCN. The latter value is in excellent agreement with the most recent experimental determination (14.8 + or - 2.0 kcal/mol).

Lee, Timothy J.↗
NASA NTRS1997

Interfacing Relativistic and Nonrelativistic Methods: A Systematic Sequence of Approximations

A systematic sequence of approximations for the introduction of relativistic effects into nonrelativistic molecular finite-basis set calculations is described. The theoretical basis for the approximations is the normalized elimination of the small component (ESC) within the matrix representation of the modified Dirac equation. The key features of the normalized method are the retention of the relativistic metric and the ability to define a single matrix U relating the pseudo-large and large component coefficient matrices. This matrix is used to define a modified set of one- and two-electron integrals which have the same appearance as the integrals of the Breit-Pauli Hamiltonian. The first approximation fixes the ratios of the large and pseudo-large components to their atomic values, producing an expansion in atomic 4-spinors. The second approximation defines a local fine-structure constant on each atomic centre, which has the physical value for centres considered to be relativistic and zero for nonrelativistic centres. In the latter case, the 4-spinors are the positive-energy kinetic al ly-balanced solutions of the Levy-Leblond equation, and the integrals involving pseudo-large component basis functions on these centres, are set to zero. Some results are presented for test systems to illustrate the various approximations.

Dyall, Ken↗
NASA NTRS1988

Theoretical study of the nitrogen atom hyperfine coupling constant

The nitrogen-atom isotropic hyperfine coupling constant A(iso) is studied as a function of improvements in both the one-particle and n-particle basis sets. The study underscores the importance of diffuse basis functions. For example, the (9s 5p) primitive set of Huzinaga (1965) augmented with an even-tempered diffuse s function yields values for A(iso) that are virtually identical to an energy-optimized (23s 12p) even-tempered set. The A(iso) constant is found to converge relatively quickly with increasing l quantum numbers: d, f, and g functions are estimated to contribute 2.5 + or - 0.2, 0.4 + or - 0.1, and 0.05 + or - 0.05 MHz, respectively. Full CI calibration calculations indicate that very high levels of correlation treatment are required for quantitative results. In addition, a strong coupling is observed between the one-particle and n-particle requirements. The best result, 10.4 MHz, is in excellent agreement with the accurate experimental value of 10.4509 MHz.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2004

Optimal Aerosol Parameterization for Remote Sensing Retrievals

We have developed a new algorithm for the retrieval of aerosol and gases from SAGE It1 solar transmission measurements. This algorithm improves upon the NASA operational algorithm in several key aspects, including solving the problem non-linearly and incorporating a new methodology for separating the contribution of aerosols and gases. In order to extract aerosol information we have built a huge database of aerosol models for both stratospheric and tropospheric aerosols, and polar stratospheric cloud particles. This set of models allows us to calculate a vast range of possible extinction spectra for aerosols. and from these, derive a set of eigenvectors which then provide the basis set used in our inversion algorithm. Our aerosol algorithm and retrievals are described in several articles (listed in References Section) published under this grant. In particular they allow us to analyze the spectral properties of aerosols and PSCs and ultimately derive their microphysical properties. We have found some considerable differences between our spectra and the ones derived from the SAGE III operational algorithm. These are interesting as they provide an independent check on the validity of published aerosol data and, in particular, on their associated uncertainties. In order to understand these differences, we are assembling independent aerosol data from other sources with which to make comparisons. We have carried out extensive comparisons of our ozone retrievals with both SAGE III and independent lidar, ozonesonde, and satellite measurements (Polyakov et al., 2004). These show very good agreement throughout the stratosphere and help to quantify differences which can be attributed to natural variation in ozone versus that produced by algorithmic differences. In the mid - upper stratosphere, agreement with independent data was generally within 5 - 20%. but in the lower stratosphere the differences were considerably larger. We believe that a large proportion of this discrepancy in the lower stratosphere is attributable to natural variation, and is also seen in comparisons between lidar and ozonesonde measurements. NO2 profiles obtained with our algorithm were compared to those obtained through the SAGE III operational algorithm and exhibited differences of 20 - 40%. Our retrieved profiles agree with the HALOE NO2 measurements significantly better than those of the operational retrieval. In other work (described below), we are extending our aerosol retrievals into the infrared regime and plan to perform retrievals from combined uv-visible-infrared spectra. This work will allow us to use the spectra to derive the size and composition of aerosols, and we plan to employ our algorithms in the analysis of PSC spectra. We are presently also developing a limb-scattering algorithm to retrieve aerosol data from limb measurements of solar scattered radiation.

Newchurch, Michael J.↗
NASA NTRS2017

MATRIX-VBS (v1.0): Implementing an Evolving Organic Aerosol Volatility in an Aerosol Microphysics Model

The gas-particle partitioning and chemical aging of semi-volatile organic aerosol are presented in a newly developed box model scheme, where its effect on the growth, composition, and mixing state of particles is examined. The volatility-basis set (VBS) framework is implemented into the aerosol microphysical scheme MATRIX (Multiconfiguration Aerosol TRacker of mIXing state), which resolves mass and number aerosol concentrations and in multiple mixing-state classes. The new scheme, MATRIX-VBS, has the potential to significantly advance the representation of organic aerosols in Earth system models by improving upon the conventional representation as non-volatile particulate organic matter, often also with an assumed fixed size distribution. We present results from idealized cases representing Beijing, Mexico City, a Finnish forest, and a southeastern US forest, and investigate the evolution of mass concentrations and volatility distributions for organic species across the gas and particle phases, as well as assessing their mixing state among aerosol populations. Emitted semi-volatile primary organic aerosols evaporate almost completely in the intermediate-volatility range, while they remain in the particle phase in the low-volatility range. Their volatility distribution at any point in time depends on the applied emission factors, oxidation by OH radicals, and temperature. We also compare against parallel simulations with the original scheme, which represented only the particulate and non-volatile component of the organic aerosol, examining how differently the condensed-phase organic matter is distributed across the mixing states in the model. The results demonstrate the importance of representing organic aerosol as a semi-volatile aerosol, and explicitly calculating the partitioning of organic species between the gas and particulate phases.

volatility-basis set↗
NASA NTRS1989

Annual and interannual variations of Earth-emitted radiation based on a 10-year data set

The method of empirical orthogonal functions (EOF) was applied to a 10-year data set of outgoing longwave radiation. Spherical harmonic functions are used as a basis set for producing equal area map results. The following findings are noted. The first EOF accounts for 66 percent of the variance. After that, each EOF accounts for only a small variance, forming a slowly converging series. The first two EOF's describe mainly the annual cycle. The third EOF is primarily the semiannual cycle although many other EOF's also contain significant semiannual parts. These results reaffirm those based on a shorter data set. In addition, a much stronger spring/fall mode was found in the central equatorial Pacific Ocean for the second EOF than was found earlier. This difference is attributed to the use of broadband radiometer data which were available for the present study. The earlier study used data from a window channel instrument which is not as sensitive to water vapor variations. The fourth EOF describes much of the 1976 to 1977 and 1982 to 1983 ENSO phenomena. There is typically a gap in the spectrum between a semiannual peak and the annual cycle for all but the first EOF. A semiannual OLR dipole straddles the Asian-Australian monsoon track.

Bess, T. Dale↗
NASA NTRS1990

Ground and lower excited states of methyl peroxy, CH3O2, radical - A computational investigation

The ground and lower excited states of methyl peroxy, CH3O2, radical have been investigated at the selected pseudofirst-order configuration interaction level by use of a double-zeta basis set. Selected singles and doubles calculations using a polarized double-zeta basis have been carried out on the two lowest states in the A-double prime symmetry. Dissociation energies with respect to CH3O2 yields CH3 + O2 and CH3O + O are computed to be 2.01 and 3.37 eV, respectively. Curve crossings between various states and photodissociation products are discussed and the dipole moment along various slices through the potential energy surface is evaluated.

Jafri, Jawed A.↗
NASA NTRS1992

Annual and interannual variations of earth-emitted radiation based on a 10-year data set

The method of empirical orthogonal functions (EOFs) was applied to a 10-yr data set of outgoing longwave radiation. Spherical harmonic functions are used as a basis set for producing equal area map results. The first EOF accounts for 66 percent of the variance. After that, each EOF accounts for only a small variance, forming a slowly converging series. The first two EOFs describe mainly the annual cycle. The third EOF is primarily the semiannual cycle although many other EOFs also contain significant semiannual parts. These results reaffirm those based on a shorter data set. In addition, a much stronger spring/fall mode was found in the central equatorial Pacific Ocean for the second EOF than was found earlier. The fourth EOF describes much of the 1976 to 1977 and 1982 to 1983 ENSO phenomena. There is typically a gap in the spectrum between a semiannual peak and the annual cycle for all but the first EOF. A semiannual OLR dipole straddles the Asian-Australian monsoon track.

Bess, T. D.↗
NASA NTRS2011

Sampling Theorem in Terms of the Bandwidth and Sampling Interval

An approach has been developed for interpolating non-uniformly sampled data, with applications in signal and image reconstruction. This innovation generalizes the Whittaker-Shannon sampling theorem by emphasizing two assumptions explicitly (definition of a band-limited function and construction by periodic extension). The Whittaker- Shannon sampling theorem is thus expressed in terms of two fundamental length scales that are derived from these assumptions. The result is more general than what is usually reported, and contains the Whittaker- Shannon form as a special case corresponding to Nyquist-sampled data. The approach also shows that the preferred basis set for interpolation is found by varying the frequency component of the basis functions in an optimal way.

Dean, Bruce H.↗
NASA NTRS1991

Dissociative recombination of the ground state of N2(+)

Large-scale calculations of the dissociative recombination cross sections and rates for the v = 0 level of the N2(+) ground state are reported, and the important role played by vibrationally excited Rydberg states lying both below and above the v = 0 level of the ion is demonstrated. The large-scale electronic wave function calculations were done using triple zeta plus polarization nuclear-centered-valence Gaussian basis sets. The electronic widths were obtained using smaller wave functions, and the cross sections were calculated on the basis of the multichannel quantum defect theory. The DR rate is calculated at 1.6 x 10 to the -7th x (Te/300) to the -0.37 cu cm/sec for Te in the range of 100 to 1000 K, and is found to be in excellent agreement with prior microwave afterglow experiments but in disagreement with recent merged beam results. It is inferred that the dominant mechanism for DR imparts sufficient energy to the product atoms to allow for escape from the Martian atmosphere.

Guberman, Steven L.↗
NASA NTRS2024

Accurate Infrared Line Lists for 20 Isotopologues of CS 2 at Room Temperature

To facilitate atmospheric and spectroscopic studies of carbon disulfide, or CS 2 , in both planetary and exoplanetary atmospheres, we adopt the “Best Theory + Reliable High-resolution Experiment” algorithm to generate semiempirical IR line lists for the 20 most abundant CS 2 isotopologues, denoted as Ames-296K. The IR lists are computed using the Ames-1 potential energy surface, refined using the experimental transition set and an ab initio dipole moment surface fitted from CCSD(T)/aug-cc-pV(T/Q/5+d)Z dipoles extrapolated to a one-particle basis set limit. The IR lists cover the range of 0–10,000 cm -1 , with an S 296K cutoff at 10 -31 cm -1 /molecule·cm -2 (abundance included). A “natural” IR line list at 296 K includes about 10 million lines of the 20 isotopologues, with their intensities scaled by the corresponding abundances. The zero-point energy, partition functions, and abundances are reported for each isotopologue. The energy levels in the global effective Hamiltonian model for 12 C 32 S 2 are adopted to improve the line position accuracy. This new IR list for the main isotopologue is denoted as A+I.296K. Reliable HITRAN2020 line positions are also utilized to improve the accuracy of the 32 S 12 C 34 S, 32 S 12 C 33 S, and 32 S 13 C 32 S isotopologue line lists. The final composite line list is validated against Pacific Northwest National Laboratory experimental cross sections, showing excellent agreement. The agreement supports the quality of the composite line list and the power of synergy between experiment and theory. The new data are proposed for use in updating and expanding the CS 2 data in HITRAN and other high-resolution IR databases. Supplementary files are available in Zenodo and AHED.

Exoplanet atmospheric composition↗
NASA NTRS1965

Lower Bounds for the Energy Levels of Anharmonic Oscillators

The lower‐bounds method presented by Löwdin in the preceding paper has been applied to oscillators perturbed by third‐ and fourth‐power terms in the potential‐energy expression. For favorable cases agreement between upper and lower bounds is easily carried to many more figures than are likely to be physically significant. In many cases the lower bounds agreed more closely to the true eigenvalue than did the corresponding upper bounds. For a given basis set, this method gives closer bounds than that of Bazley and Fox, except for energy levels too high to be satisfactorily treated in the given basis. The only disadvantage found was that for close bounds double precision proved necessary, indicating more than ordinary loss of computational accuracy.

Reid, Charles E.↗
NASA NTRS1993

Accurate ab initio quartic force fields for the ions HCO(+) and HOC(+)

The quartic force fields of HCO(+) and HOC(+) have been computed using augmented coupled cluster methods and basis sets of spdf and spdfg quality. Calculations on HCN, CO, and N2 have been performed to assist in calibrating the computed results. Going from an spdf to an spdfg basis shortens triple bonds by about 0.004 A, and increases the corresponding harmonic frequency by 10-20/cm, leaving bond distances about 0.003 A too long and triple bond stretching frequencies about 5/cm too low. Accurate estimates for the bond distances, fundamental frequencies, and thermochemical quantities are given. HOC(+) lies 37.8 +/- 0.5 kcal/mol (0 K) above HCO(+); the classical barrier height for proton exchange is 76.7 +/- 1.0 kcal/mol.

Martin, J. M. L.↗
NASA NTRS1987

Theoretical D(0) for NH(X3Sigma-)

A value of 3.37 + or - 0.03 eV is recommended for the D(0) of the X3Sigma(-) state of NH. The value of 3.34 eV computed directly from CAS SCF/MRSD CI calculations in a (5s4p3d2f1g/4s3p2d) contracted Gaussian basis has been corrected for basis set incompleteness based on analogous calculations on CH and OH where D(0) is accurately known. Equivalent full CI calculations on the ground states of CH, NH and OH in a (4s3p2d/2s1p) basis provide strong support for the 0.03 eV extrapolation of the D(0) for NH.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1997

Formation of Carbon Nanotube Based Gears: Quantum Chemistry and Molecular Mechanics Study of the Electrophilic Addition of o-Benzyne to Fullerenes, Graphene, and Nanotubes

Considerable progress has been made in recent years in chemical functionalization of fullerene molecules. In some cases, the predominant reaction products are different from those obtained (using the same reactants) from polycyclic aromatic hydrocarbons (PAHs). One such example is the cycloaddition of o-benzyne to C60. It is well established that benzyne adds across one of the rings in naphthalene, anthracene and other PAHs forming the [2+4] cycloaddition product (benzobicyclo[2.2.2.]-octatriene with naphthalene and triptycene with anthracene). However, Hoke et al demonstrated that the only reaction path for o-benzyne with C60 leads to the [2+2] cycloaddition product in which benzyne adds across one of the interpentagonal bonds (forming a cyclobutene ring in the process). Either reaction product results in a loss of aromaticity and distortion of the PAH or fullerene substrate, and in a loss of strain in the benzyne. It is not clear, however, why different products are preferred in these cases. In the current paper, we consider the stability of benzyne-nanotube adducts and the ability of Brenner's potential energy model to describe the structure and stability of these adducts. The Brenner potential has been widely used for describing diamondoid and graphitic carbon. Recently it has also been used for molecular mechanics and molecular dynamics simulations of fullerenes and nanotubes. However, it has not been tested for the case of functionalized fullerenes (especially with highly strained geometries). We use the Brenner potential for our companion nanogear simulations and believe that it should be calibrated to insure that those simulations are physically reasonable. In the present work, Density Functional theory (DFT) calculations are used to determine the preferred geometric structures and energetics for this calibration. The DFT method is a kind of ab initio quantum chemistry method for determining the electronic structure of molecules. For a given basis set expansion, it is comparable in accuracy to the MP2 method (better than Hartree Fock, but less accurate than more extensive electron correlation methods such as MP4 or CCSD). However, for systems with large numbers of basis functions it more efficient than any other methods that include electron correlation effects. In this presentation we show the results of DFT calculations for the reaction of benzyne with naphthalene, C60, and nanotube models. We compare energies for [2+2] and [2+4] cycloaddition products. The preferred products for the naphthalene and C60 reactions have been determined by experiment and, thus, these cases serve as a validation of our quantum chemical approach. We also compare the DFT and Brenner potential results. Finally we can predict the likelihood of reaction between benzyne and nanotubes.

Jaffe, Richard↗
NASA NTRS1986

Calculated ground state potential surface and excitation energies for the copper trimer

In the context of their relevance to catalysis and to materials science problems, transition metals and transition metal (TM) compounds are currently of considerable interest, and studies have been conducted of the copper trimer, Cu3. The present investigation is concerned with a study of the ground state surface and several groups of excited states in order to improve the understanding of the spectroscopy of Cu3. Differences of the current study from previous investigations are related to an employment of larger basis sets and a more extensive electron correlation. This was done with the objective to obtain a more accurate definition of the ground state surface. Features of the bonding in the copper dimer are considered to obtain a basis for an understanding of the copper trimer. Attention is given to calculational details, the ground state surface, and calculated vertical excitation energies. The results of SCF/SDCI calculations are reported for portions of the ground surface, for two groups of excited states, and for the ionization potential of Cu3.

Walch, S. P.↗