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At least 217 records · Page 12

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NASA NTRS1994

Intermediates in the Formation of Aromatics in Hydrocarbon Combustion

The formation of the first benzene ring is believed to be the rate limiting step in soot formation. Two different mechanisms have been proposed for formation of cyclic C6 species. The first involves the reaction of two acetylenes to give CH2CHCCH (vinyl acetylene), the loss of a H to give CHCHCCH (n-C41-13) or CH2CCCH (iso-C4H3), and addition of another acetylene to n-C4H3, followed by ring closure to give phenyl radical. Miller and Melius argue that only n-C4H3 leads to phenyl radical and since iso-C4H3 is more stable than n-C4H3 this mechanism is unlikely. An alternative mechanism proposed by them is formation of benzene from the dimerization of two CH2CCH (propargyl) radicals (formed by the reaction of singlet methylene with C2H2). We report reaction pathways and accurate energetics (from CASSCF/internally contracted CI calculations) for the reactions of CH(pi-2) and CH2-1 with acetylene, the reaction of vinylidene with acetylene, and the reaction of n-C4H3 and iso-C4H3 with acetylene. These calculations identify two new reactive intermediates CHCHCH ( a A"-2 ground state in Cs symmetry; spin coupling is a doublet from three singly occupied orbitals) and CHCCH (B-3 ground state in C2 symmetry) from the reaction of CH with acetylene. These species dimerize with no barrier to form benzene and para-benzyne, respectively. CHCCH is proposed as a reactive intermediate which can add to benzene to give higher polynuclear aromatic hydrocarbons or fullerenes. The addition of a C3H2 unit releases two C-C bond energies and thus the resulting addition product contains sufficient energy to break several CH bonds leading to a reduction in the H to C ratio as the cluster size increases. It is found that iso-C4H3 adds to acetylene to initially give a fulvene radical but that this species rearranges to phenyl radical. Thus, the reaction of acetylene with iso-C4H3 does lead to phenyl radical and the cyclization pathway may also contribute to formation of the initial benzene ring.

Walch, Stephen P.↗

NASA NTRS1986

Studies of interstellar vibrationally-excited molecules

Several molecules thus far have been detected in the ISM in vibrationally-excited states, including H2, SiO, HC3N, and CH3CN. In order for vibrational-excitation to occur, these species must be present in unusually hot and dense gas and/or where strong infrared radiation is present. In order to do a more thorough investigation of vibrational excitation in the interstellar medium (ISM), studies were done of several mm-wave transitions originating in excited vibrational modes of HCN, an abundant interstellar molecule. Vibrationally-excited HCN was recently detected toward Orion-KL and IRC+10216, using a 12 meter antenna. The J=3-2 rotational transitions were detected in the molecule's lowest vibrational state, the bending mode, which is split into two separate levels, due to l-type doubling. This bending mode lies 1025K above ground state, with an Einstein A coefficient of 3.6/s. The J=3-2 line mode of HCN, which lies 2050K above ground state, was also observed toward IRC+10216, and subsequently in Orion-KL. Further measurements of vibrationally-excited HCN were done using a 14 meter telescope, which include the observations of the (0,1,0) and (0,2,0) modes towards Orion-KL, via their J=3-2 transitions at 265-267 GHz. The spectrum of the J=3-2 line in Orion taken with the 14 meter telescope, is shown, along with a map, which indicates that emission from vibrationally-excited HCN arises from a region probably smaller than the 14 meter telescope's 20 arcsec beam.

Ziurys, L. M.↗

NASA NTRS1994

What is the Structure of FeC5H6(+)?

Calculations performed using both density functional theory (DFT) and the modified coupled-pair functional (MCPF) approach show that FeC5H6(+) is more stable than HFeC5H5(+) by about 10 kcal/mol. The ground state of FeC5H6(+) is a quartet state derived from the 3d(sup 7) occupation of Fe+. For HFeC5H6(+), the MCPF 5 approach yields a sextet ground state while DFT yields a quartet; however, these two states are close in energy at both levels of theory.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1996

Theoretical Studies of Some HEDM Species: Cyclic O4, Cyclic O3 and Cubane

Calculations have been carried out for the HEDM species (cyclic O4, cyclic O3, and cubane) using CASSCF/derivative and CASSCF/ICCI methods. Cyclic O4 is of interest both as a potential HEDM species and because of its possible role in the ozone deficit problem in atmospheric chemistry. We have studied the pathway for decomposition from the D(2d) minimum and also have found the approximate location of the singlet triplet crossing. The barrier to decomposition is found to be about 9 kcal/mol and is not limited by the singlet triplet crossing. For cyclic O3 we have focused on the crossings between the lowest five surfaces (X(1)A(1), s(1)A(1), (1)A(2), (1)B(1), and (1)B(2)) to provide some insight into ways to form cyclic O3 photochemically. The crossing region between the X(1)A(1) and 2(1)A(1) surfaces is in agreement with the work of Xantheas et al. The calculations show that vertical excitation from the ground state to the (1)A(2) state leads to a crossing with the (1)A(1) manifold near the crossing region of the X(1)A(1) and 2(1)A(1) surfaces. We have studied the decomposition pathways for cubane to benzene plus acetylene and to cyclooctatetraene. We have also studied the ground and excited states for the photochemical ring closure step. The state which closes to cubane can be described as a double triplet pi to pi* excitation with respect to the ground state. Thus, this state has only a small oscillator strength with respect to the ground state. However, there is a singlet pi to pi* state at nearly the same energy and excitation to this state followed by intersystem crossing could lead to the triplet pi to pi* state.

Walch, Stephen P.↗

NASA NTRS1987

Pumping the stellar hydroxyl maser

IRAS far-IR flux data for 163 OH maser stars were analyzed to quantify the contributions 35 and 53 microns inversions make to pumping of the hydroxyl maser. The 35 microns transition is from the 3,3 ground state to the 1,5 rotationally excited level and subsequent decay; the 53 microns transition is a change from the ground state to the 1,3 excited level and relaxation. The stars examined included Mira, short period semi-regular and long-period semi-regular variables. Both transition lines had rough parity in contributing to the approximately 8 percent pumping efficiency at 1612 MHz. However, the individual contributions of the lines could not be determined for the stellar population studied.

Dickinson, Dale F.↗

NASA NTRS1988

The fluorescence of cometary OH

A new solar spectral atlas, improved oscillator strengths, and additional transitions have been incorporated in calculations of the fluorescent equilibrium of the OH molecule in comets as a function of heliocentric distance and radial velocity. Comparisons of detailed, ultraviolet band profiles have been made with the observed, high-resolution spectra of eight comets. While a purely fluorescent equilibrium calculation is sufficient to reproduce the major variations seen in the band structure from one comet to another, some collisional quenching of the inversion of the X2II3/2 Lambda-doublet ground state is required to match the detailed features. The relative population inversion of the upper and lower levels of the ground state is also calculated as a function of both distance and velocity, with the results being consistent with 18 cm radio observations. Predictions of the infrared OH vibrational bands are made; the 1-0 band should be observable if a sufficiently high spectral resolution is employed.

Schleicher, David G.↗

NASA NTRS1987

An initio calculations on C2, Si2, and SiC

Full-configuration-interaction (FCI) calculations have been performed for the Z 1Sigma(g)(+), a 3Pi(u), and b 3Sigma(g)(-) states of C2 and the X 3Sigma(g)(-) and A 3Pi(u) states of Si2 in valence double-zeta plus polarization one-particle basis sets. By carrying out the CASSCF multireference singles plus doubles CI (MRCI) procedure in a very large Gaussian basis set and correcting for errors with the FCI, the triplet-triplet separation in C2 is reproduced to within 47/cm. Analogous calculations on Si2 definitively determine the ground state to be 3Sigma(g)(-); the 3Pi(u) state is only 440 + or - 100/cm higher in energy. For the SiC molecule, which has never been observed spectroscopically but is believed to be an important component in carbon stars and to be present in interstellar space, the A 3Sigma(-) state is nearly 4000/cm above the X 3Pi ground state.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1982

Picosecond flash spectroscopic studies on ultraviolet stabilizers and stabilized polymers

Spectroscopic and excited state decay kinetics are reported for monomeric and polymeric forms of ultraviolet stabilizers in the 2-(2'-hydroxyphenyl)-benzotriazole and 2-hydroxybenzophenone classes. For some of these molecules in various solvents at room temperature, (1) ground state absorption spectra, (2) emission spectra, (3) picosecond time-resolved transient absorption spectra, (4) ground state absorption recovery kinetics, (5) emission kinetics, and (6) transient absorption kinetics are reported. In the solid state at low temperatures, emission spectra and their temperature dependent kinetics up to approximately 200K as well as, in one case, the 12K excitation spectra of the observed dual emission are also reported.

Scott, G. W.↗

NASA NTRS1997

Ion-Atom Cold Collisions and Atomic Clocks

Collisions between ultracold neutral atoms have for some time been the subject of investigation, initially with hydrogen and more recently with laser cooled alkali atoms. Advances in laser cooling and trapping of neutral atoms in a Magneto-Optic Trap (MOT) have made cold atoms available as the starting point for many laser cooled atomic physics investigations. The most spectacularly successful of these, the observation of Bose-Einstein Condensation (BEC) in a dilute ultra-cold spin polarized atomic vapor, has accelerated the study of cold collisions. Experimental and theoretical studies of BEC and the long range interaction between cold alkali atoms is at the boundary of atomic and low temperature physics. Such studies have been difficult and would not have been possible without the development and advancement of laser cooling and trapping of neutral atoms. By contrast, ion-atom interactions at low temperature, also very difficult to study prior to modern day laser cooling, have remained largely unexplored. But now, many laboratories worldwide have almost routine access to cold neutral atoms. The combined technologies of ion trapping, together with laser cooling of neutrals has made these studies experimentally feasible and several very important, novel applications might come out of such investigations . This paper is an investigation of ion-atom interactions in the cold and ultra-cold temperature regime. Some of the collisional ion-atom interactions present at room temperature are very much reduced in the low temperature regime. Reaction rates for charge transfer between unlike atoms, A + B(+) approaches A(+) + B, are expected to fall rapidly with temperature, approximately as T(sup 5/2). Thus, cold mixtures of atoms and ions are expected to coexist for very long times, unlike room temperature mixtures of the same ion-atom combination. Thus, it seems feasible to cool ions via collisions with laser cooled atoms. Many of the conventional collisional interactions, exploited as a useful tool at room temperature and higher, are greatly enhanced at low energy. For example, collisional spin transfer from one species of polarized atoms to another has long been a useful method for polarizing a sample of atoms where no other means was available. Because optical pumping cannot be used to polarize the nuclear spin of Xe-129 or He-3 (for use in nmr imaging of the lungs), the nuclear spins are polarized via collisions with an optically pumped Rb vapor in a cell containing both gases. In another case, a spin polarized thermal Cs beam was used to polarize the hyperfine states of trapped He(+)-3 ions in order to measure their hyperfine clock transition frequency. The absence of an x-ray light source to optically pump the ground state of the He(+)-3 ion necessitated this alternative state preparation. Similarly, Cd(+) and Sr(+) ions were spin-oriented via collisions in a cell with optically pumped Rb vapor. Resonant RF spin changing transitions in the ground state of the ions were detected by changes in the Rb resonance light absorption. Because cold collision spin exchange rates scale with temperature as T(sup -1/2) this technique is expected to be a far more powerful tool than the room temperature counterpart. This factor of 100 or more enhancement in spin exchange reaction rates at low temperatures is the basis for a novel trapped ion clock where laser cooled neutrals will cool, state select and monitor the ion clock transition. The advantage over conventional direct laser cooling of trapped ions is that the very expensive and cumbersome UV laser light sources, required to excite the ionic cooling transition, are effectively replaced by simple diode lasers.

Prestage, John D.↗

NASA NTRS1987

Chaotic nature of the spin-glass phase

The microscopic structure of the ordered phase of spin glasses is investigated theoretically in the framework of the T = 0 fixed-point model (McMillan, 1984; Fisher and Huse, 1986; and Bray and Moore, 1986). The sensitivity of the ground state to changes in the interaction strengths at T = 0 is explored, and it is found that for sufficiently large length scales the ground state is unstable against arbitrarily weak perturbations to the bonds. Explicit results are derived for d = 1, and the implications for d = 2 and d = 3 are considered in detail. It is concluded that there is no hidden order pattern for spin glasses at all T less than T(C), the ordered-phase spin correlations being chaotic functions of spin separation at fixed temperature or of temperature (for a given pair of spins) at scale lengths L greater than (T delta T) exp -1/zeta, where zeta = d(s)/2 - y, d(s) is the interfacial fractal dimension, and -y is the thermal eigenvalue at T = 0.

Bray, A. J.↗

NASA NTRS1966

Excitation of H atoms by fast protons.

Excitation of ground state hydrogen atoms by fast protons, evaluating total Born cross section in limit of infinitely massive protons

PROTON↗

NASA NTRS1973

Selective reabsorption leading to multiple oscillations in the 8446-A atomic-oxygen laser.

Laser oscillation of atomic oxygen at 8446 A occurs in four closely spaced lines with peculiar intensity ratios, all detuned from the atomic center frequencies of the three fine-structure transitions. These anomalies are caused by the selective reabsorption of resonance radiation from the lower laser level by ground-state oxygen atoms. The selectivity results from the fact that the velocity distribution of the laser levels is considerably wider than that of the ground state, because of the dissociative mode of production of excited oxygen atoms. Possible extension of this mechanism to the atomic-hydrogen system is discussed.

Feld, M. S.↗

NASA NTRS1974

X-alpha calculation of transition energies in multiply ionized atoms

It is shown that the accuracy of calculations can be improved if appropriate (different) values of alpha are used for each configuration. Alternatively, the Slater Transition state can be used, wherein a total energy difference is related to a difference in single electron eigenvalues. By a series expansion, the value of alpha for an excited configuration can be related to its value for the ground state configuration. The terms Delta alpha (delta Epsilon/delta alpha) exhibit a similar dependence on atomic number as the ground state values of alpha. Results of sample calculations are reported and compared with experiment.

Ringers, D. A.↗

NASA NTRS1991

Ab initio study of C + H3+ reactions

The reaction C + H3+ --> CH(+) + H2 is frequently used in models of dense interstellar cloud chemistry with the assumption that it is fast, i.e. there are no potential energy barriers inhibiting it. Ab initio molecular orbital study of the triplet CH3+ potential energy surface (triplet because the reactant carbon atom is a ground state triplet) supports this hypothesis. The reaction product is 3 pi CH+; the reaction is to exothermic even though the product is not in its electronic ground state. No path has been found on the potential energy surface for C + H3+ --> CH2(+) + H reaction.

NASA Discipline Exobiology↗

NASA NTRS1987

Near Hartree-Fock quality GTO basis sets for the second-row atoms

Energy optimized, near Hartree-Fock quality Gaussian basis sets ranging in size from (17s12p) to (20s15p) are presented for the ground states of the second-row atoms for Na(2P), Na(+), Na(-), Mg(3P), P(-), S(-), and Cl(-). In addition, optimized supplementary functions are given for the ground state basis sets to describe the negative ions, and the excited Na(2P) and Mg(3P) atomic states. The ratios of successive orbital exponents describing the inner part of the 1s and 2p orbitals are found to be nearly independent of both nuclear charge and basis set size. This provides a method of obtaining good starting estimates for other basis set optimizations.

Partridge, Harry↗

NASA NTRS1987

Near Hartree-Fock quality GTO basis sets for the second-row atoms

Partridge, Harry↗

NASA NTRS1989

Theoretical studies of the transition metal-carbonyl systems MCO and M(CO)2, M = Ti, Sc, and V

Large Gaussian basis sets and an electron correlation treatment are used in ab initio calculations on the transition metal-carbonyl systems MCO and N(CO)2 for M = Ti, Sc, and V. The results show that high-spin ground states are favored for the monocarbonyl molecules, and that for the dicarbonyl molecules there is a competition between high, intermediate, and low spin states which are very close in energy. Dissociation energies of 0.62 eV for Ti-CO and 1.02 for Ti(CO)2 are found, relative to the ground state Ti atomic asymptote and CO 1Sigma(+). The binding energy per carbonyl for the three metal atoms is shown to be significantly lower for the dicarbonyl than for the the monocarbonyl molecules.

Barnes, Leslie A.↗

NASA NTRS1986

Ab initio calculations on the positive ions of the alkaline-earth oxides, fluorides, and hydroxides

Theoretical dissociation energies are presented for the alkaline-earth fluoride, hydroxide, and oxide positive ions that are considered to be accurate to 0.1-0.2 eV. The r(e) for the positive ions are found to be consistently shorter than the corresponding neutrals by 0.07 + or -0.02 A. The bonding in the ground states is demonstrated to be of predominantly M + 2 X - character. The a 3 Pi and A 1 Pi are found to lie considerably above the X 1 Sigma + ground states of the alkaline-earth fluoride and hydroxide positive ions. The overall agreement of the theoretical ionization potentials with the available experimental appearance potentials is satisfactory; these values should represent the most accurate and consistent set available.

Partridge, H.↗