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At least 163 records · Page 9
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Quantum mechanical algebraic variational methods for inelastic and reactive molecular collisions

The quantum mechanical problem of reactive or nonreactive scattering of atoms and molecules is formulated in terms of square-integrable basis sets with variational expressions for the reactance matrix. Several formulations involving expansions of the wave function (the Schwinger variational principle) or amplitude density (a generalization of the Newton variational principle), single-channel or multichannel distortion potentials, and primitive or contracted basis functions are presented and tested. The test results, for inelastic and reactive atom-diatom collisions, suggest that the methods may be useful for a variety of collision calculations and may allow the accurate quantal treatment of systems for which other available methods would be prohibitively expensive.

Schwenke, David W.↗
NASA NTRS1992

Concerted hydrogen atom exchange between three HF molecules

The termolecular reaction involving concerted hydrogen-atom exchange between three HF molecules was investigated with particular attention given to the effects of correlation at the various stationary points along the reaction. Using large segmented Gaussian basis sets to locate the (HF)3 stationary points at the SCF level, the geometries of the stable hydrogen-bonded trimer, which is of C(3h) symmetry, were located, together with the transition state for hydrogen exchange, which is of D(3h) symmetry. Then, using a large atomic natural orbital basis and correlating all valence electrons, the energetics of the exchange reaction were evaluated at the correlated level.

Komornicki, Andrew↗
NASA NTRS1993

Accurate Quartic Force Fields and Vibrational Frequencies for HCN and HNC

The quartic force fields of HCN and HNC are determined using atomic natural orbital one-particle basis sets of spdf/spd and spdfg/spdf quality in conjunction with the CCSD(T) electron correlation method (singles and doubles coupled-cluster theory plus a perturbational estimate of the effects of connected triple excitations). The HCN force field is in good agreement with a recent experimentally derived force field and also with the force field recently computed by Wong and Bacskay. On the basis of the good agreement obtained for HCN, it is argued that the ab initio quartic force field for HNC is superior to a prior force field derived from experiment. The harmonic frequencies of HNC are predicted to be 3822 +/- 10,472 +/- 5, and 2051 +/-10/cm for omega1, omega2, and omega3, respectively; the experimentally derived values are above these values and fall outside the estimated uncertainties. Using the quartic force field, spectroscopic constants are predicted for HNC based on a vibrational second-order perturbation theory analysis. It is also asserted that the gas-phase fundamental v(sub 3) for HNC is slightly lower than the matrix isolation value. The range of validity of the quartic force fields is investigated by comparison of variational vibrational energies computed with the quartic force fields to those obtained from our recently reported global HCN/HNC potential energy surface and also to experimental data.

Lee, Timothy J.↗
NASA NTRS1993

Accurate Quartic Force Fields and Vibrational Frequencies for HCN and HNC

The quartic force fields of HCN and HNC are determined using atomic natural orbital one-particle basis sets of spdf/spd and spdfg/spdf quality in conjunction with the CCSD(T) electron correlation method (singles and doubles coupled-cluster theory plus a perturbation estimate of the effects of connected triple excitations). The HCN force field is in good agreement with a recent experimentally derived force field and also with the force field recently computed by Wong and Bacskay. On the basis of the good agreement obtained for HCN, it is argued that the ab initio quartic force field for HNC is superior to a prior force field derived from experiment. The harmonic frequencies of HNC are predicted to be 3822 +/- 10, 472 +/- 5, and 2051 +/- 10 cm(exp -1) for omega(sub 1), omega(sub 2), and omega(sub 3), respectively; the experimentally derived values are above these values and fall outside the estimated uncertainties. Using the quartic force field, spectroscopic constants are predicted for HNC based on a vibrational second-order perturbation theory analysis. It is also asserted that the gas-phase fundamental nu(sub 3) for HNC is slightly lower than the matrix isolation value. The range of validity of the quartic force fields is investigated by comparison of variational vibrational energies computed with the quartic force fields to those obtained from our recently reported global HCN/HNC potential energy surface and also to experimental data.

Lee, Timothy J.↗
NASA NTRS1990

On the dissociation energy of Mg2

The bonding in the X 1Sigma(+)g state of Mg2 is investigated using near-complete valence one-particle Slater and Gaussian basis sets containing up to h functions. It is shown that the four-electron complete CI limit can be approached using a sequence of either second-order CI (SOCI) or interacting correlated fragment (ICF) calculations. At the valence level, the best estimate of the dissociation energy D(e) was 464/cm. This is a lower limit and is probably within 5/cm of the complete basis value.

Partridge, Harry↗
NASA NTRS1983

Supplemental basis functions for the second transition row elements

It is noted that for molecular calculations, the basis sets presented by Huzinaga (1977) need to be augmented by (1) 5p functions to describe the 5s - 5p near degeneracy; (2) a diffuse 4d function to provide for a balanced description of the 5s2 4dn, 5s1 4d(n+1), and 4d(n+2) states of the atom; and (3) a set of 4f functions to correlate the 4d functions. Here, the diffuse 4d function is similar in function to the diffuse 3d function for the first transition row elements recommended by Hay (1977). A table is included giving the optimized values for the diffuse 4d, the 5p, and 4f (STO exponent) functions. The diffuse 4d function and the 5p functions are optimized at the SCF level on the basis of the 5s1 4d(n+1) state (except for Pd, which is optimized for the 4d10 state) and the 5s1 5p1 4dn state, respectively. The table also gives the energies and the atomic symmetries for each of the SCF calculations.

Walch, S. P.↗
NASA NTRS1986

An ab initio investigation of possible intermediates in the reaction of the hydroxyl and hydroperoxyl radicals

Ab initio quantum chemical techniques have been used to investigate covalently-bonded and hydrogen-bonded species that may be important intermediates in the reaction of hydroxyl and hydroperoxyl radicals. Stable structures of both types were identified. Basic sets of polarized double-zeta quality and large scale configuration interaction wave functions have been utilized. Based upon electronic energies, the covalently-bonded HOOOH species is found to be 26.4 kcal/mol more stable than the OH and HO2 radicals. Similarly, the hydrogen-bonded HO-HO2 species is found to have an electronic energy 4.7 kcal/mol below that of the component radicals, after correction is made for the basis set superposition error. The hydrogen-bonded form is found to be planar, to possess one relatively 'normal' hydrogen bond, and to have lowest energy 3A-prime and 1A-prime states that are essentially degenerate. The 1A-double prime and 3A-double prime excited states produced by rotation of the unpaired OH electron into the molecular plane are found to be very slightly bound.

Jackels, C. F.↗
NASA NTRS1991

Improved techniques for outgoing wave variational principle calculations of converged state-to-state transition probabilities for chemical reactions

Improved techniques and well-optimized basis sets are presented for application of the outgoing wave variational principle to calculate converged quantum mechanical reaction probabilities. They are illustrated with calculations for the reactions D + H2 yields HD + H with total angular momentum J = 3 and F + H2 yields HF + H with J = 0 and 3. The optimization involves the choice of distortion potential, the grid for calculating half-integrated Green's functions, the placement, width, and number of primitive distributed Gaussians, and the computationally most efficient partition between dynamically adapted and primitive basis functions. Benchmark calculations with 224-1064 channels are presented.

Mielke, Steven L.↗
NASA NTRS2006

Application of p-Multigrid to Discontinuous Galerkin Formulations of the Poisson Equation

We investigate p-multigrid as a solution method for several different discontinuous Galerkin (DG) formulations of the Poisson equation. Different combinations of relaxation schemes and basis sets have been combined with the DG formulations to find the best performing combination. The damping factors of the schemes have been determined using Fourier analysis for both one and two-dimensional problems. One important finding is that when using DG formulations, the standard approach of forming the coarse p matrices separately for each level of multigrid is often unstable. To ensure stability the coarse p matrices must be constructed from the fine grid matrices using algebraic multigrid techniques. Of the relaxation schemes, we find that the combination of Jacobi relaxation with the spectral element basis is fairly effective. The results using this combination are p sensitive in both one and two dimensions, but reasonable convergence rates can still be achieved for moderate values of p and isotropic meshes. A competitive alternative is a block Gauss-Seidel relaxation. This actually out performs a more expensive line relaxation when the mesh is isotropic. When the mesh becomes highly anisotropic, the implicit line method and the Gauss-Seidel implicit line method are the only effective schemes. Adding the Gauss-Seidel terms to the implicit line method gives a significant improvement over the line relaxation method.

Helenbrook, B. T.↗
NASA NTRS2016

Electromagnetic Basis of Metabolism and Heredity

Living organisms control their cellular biological clocks to maintain functional oscillation of the redox cycle, also called the "metabolic cycle" or "respiratory cycle". Organization of cellular processes requires parallel processing on a synchronized time-base. These clocks coordinate the timing of all biochemical processes in the cell, including energy production, DNA replication, and RNA transcription. When this universal time keeping function is perturbed by exogenous induction of reactive oxygen species (ROS), the rate of metabolism changes. This causes oxidative stress, aging and mutations. Therefore, good temporal coordination of the redox cycle not only actively prevents chemical conflict between the reductive and oxidative partial reactions; it also maintains genome integrity and lifespan. Moreover, this universal biochemical rhythm can be disrupted by ROS induction in vivo. This in turn can be achieved by blocking the electron transport chain either endogenously or exogenously by various metabolites, e.g. hydrogen sulfide (H2S), highly diffusible drugs, and carbon monoxide (CO). Alternatively, the electron transport in vivo can be attenuated via a coherent or interfering transfer of energy from exogenous ultralow frequency (ULF) and extremely low frequency (ELF) electromagnetic (EM) fields, suggesting that-on Earth-such ambient fields are an omnipresent (and probably crucially important) factor for the time-setting basis of universal biochemical reactions in living cells. Our work demonstrated previously un-described evidence for quantum effects in biology by electromagnetic coupling below thermal noise at the universal electron transport chain (ETC) in vivo.

Electromagnetic↗
NASA NTRS1967

Confirmation of the predicted Hartree-Fock limit in BeH sub 2.

We have recently estimated the total energy of the BeH 2 molecule as -15.918 ± 0.015 au. One of the steps in the analysis was to estimate the difference between the SCF energies computed with a minimal basis set of Slater orbits and with the best possible single-determinant wave function, the so-called Hartree-Fock limit and was predicted to be -15.773 ± 0.007 au for BeH 2 .

Molecular energy↗
NASA NTRS1975

Many-body-theory study of lithium photoionization

A detailed theoretical calculation is carried out for the photoionization of lithium at low energies within the framework of Brueckner-Goldstone perturbational approach. In this calculation extensive use is made of the recently developed multiple-basis-set technique. Through this technique all second-order perturbation terms, plus a number of important classes of terms to infinite order, have been taken into account. Analysis of the results enables one to resolve the discrepancies between two previous works on this subject. The detailed calculation also serves as a test on the convergence of the many-body perturbation-expansion approach.

Chang, T. N.↗
NASA NTRS1975

Theoretical description of the diimide molecule

The N2H2 molecule is only metastable and as a consequence is not well characterized experimentally. Therefore, we have carried out extensive Hartree-Fock calculations in order to determine equilibrium geometries, one-electron properties, and the relative energies of the cis and trans isomers. In addition, Hartree-Fock and multiconfiguration calculations were carried out to determine the mechanism for isomerization. The trans isomer was found to be 6.6 kcal/mole more stable than the cis form using a basis set which included polarization functions. The lowest energy path found for isomerization occurred by inversion about one nitrogen (rather than rotation about the NN bond) with an activation energy of 47 kcal/mole. Excitation energies for the lowest singlet and triplet excited states are also presented.

Winter, N. W.↗
NASA NTRS1975

Rotational excitation in H2-H2 collisions - Close-coupling calculations

Rotational excitation in molecule-molecule collisions has been treated for the first time by accurate quantum close-coupling scattering calculations, employing an expansion basis set of two to three rotational levels for each molecule and correctly accounting for exchange of identical particles. Elastic and inelastic cross sections have been computed for collisions of para-para, ortho-ortho, and para-ortho hydrogen molecules assuming an intermolecular potential suggested previously. The accuracy of recent 'effective potential' calculations is demonstrated by comparison with the exact quantum results.

Green, S.↗
NASA NTRS1975

Use of LANDSAT imagery for wildlife habitat mapping in northeast and east central Alaska

The author has identified the following significant results. Two scenes were analyzed by applying an iterative cluster analysis to a 2% random data sample and then using the resulting clusters as a training set basis for maximum likelihood classification. Twenty-six and twenty-seven categorical classes, respectively resulted from this process. The majority of classes in each case were quite specific vegetation types; each of these types has specific value as moose habitat.

Lent, P. C.↗
NASA NTRS1976

MCSCF potential energy surface for photodissociation of formaldehyde

The ground state potential energy surface for the dissociation of formaldehyde (H2CO to H2 and CO) is calculated with the ab initio MCSCF method with an extended (4-31G) basis set. The location, barrier height, and force constants of the transition state are determined, and the normal coordinate analysis is carried out. The calculated barrier height is 4.5 eV. Based on the calculated quantities, the detailed mechanism of the photochemical dissociation is discussed.

Jaffe, R. L.↗