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At least 271 records · Page 15
All sourcesNASA NTRSDOE OSTI
NASA NTRS2000

A semiempirical study for the ground and excited states of free-base and zinc porphyrin-fullerene dyads

The ground and excited states of a covalently linked porphyrin-fullerene dyad in both its free-base and zinc forms (D. Kuciauskas et al., J. Phys. Chem. 100 (1996) 15926) have been investigated by semiempirical methods. The excited-state properties are discussed by investigation of the character of the molecular orbitals. All frontier MOs are mainly localized on either the donor or the acceptor subunit. Thus, the absorption spectra of both systems are best described as the sum of the spectra of the single components. The experimentally observed spectra are well reproduced by the theoretical computations. Both molecules undergo efficient electron transfer in polar but not in apolar solvents. This experimental finding is explained theoretically by explicitly considering solvent effects. The tenth excited state in the gas phase is of charge-separated character where an electron is transferred from the porphyrin donor to the fullerene acceptor subunit. This state is stabilized in energy in polar solvents due to its large formal dipole moment. The stabilization energy for an apolar environment such as benzene is not sufficient to lower this state to become the first excited singlet state. Thus, no electron transfer is observed, in agreement with experiment. In a polar environment such as acetonitrile, the charge-separated state becomes the S, state and electron transfer takes place, as observed experimentally. The flexible single bond connecting both the donor and acceptor subunits allows free rotation by ca. +/- 30 degrees about the optimized ground-state conformation. For the charge-separated state this optimized geometry has a maximum dipole moment. The geometry of the charge-separated state thus does not change relatively to the ground-state conformation. The electron-donating properties of porphyrin are enhanced in the zinc derivative due to a reduced porphyrin HOMO-LUMO energy gap. This yields a lower energy for the charge-separated state compared to the free-base dyad.

Bridged Compounds/chemistry↗
NASA NTRS1991

An ab initio study of Fe(CO)n, n = 1,5, and Cr(CO)6

Ab initio calculations have been performed for Cr(CO)6 and Fe(CO)n, n = 1,5. Basis sets of better than double zeta quality are used, and correlation is included using the modified coupler-pair functional method. The computed geometries and force constants are in reasonable agreement with experiment. The sequential bond dissociation energies of CO from Fe(CO)5 are estimated to be: 39, 31, 25, 22, and greater than 5 kcal/mol. It is noted that the first bond dissociation energy is relative to the singlet ground state of Fe(CO)5 and the lowest singlet state of Fe(CO)4, whereas the second is relative to the ground triplet states of Fe(CO)4 and Fe(CO)3. In addition, the binding energy for Fe-CO would be modified to 18 kcal/mol if dissociation occurred to the Fe(5F) excited state asymptote. The CO binding energies for Fe and Cr are found to be in poorer agreement with experiment than those found in a previous study on Ni(CO)4. The origins of this difference are discussed.

Barnes, Leslie A.↗
NASA NTRS1988

On the electron affinities of the Ca, Sc, Ti and Y atoms

For the Ca, Sc, Ti and Y atoms calculations are performed for the ground states of the neutrals and the ground and several low-lying excited states of the negative ions. Overall the computed electron affinities are in good accord with experiment. The calculations show the rapid stabilization of the 3d orbital relative to the 4p as the nuclear charge increases. The 3F(0) and 3D(0) terms are found to be close in energy in Sc(-) and in Y(-). This confirms earlier speculation that some of the peaks in the photodetachment spectra of Y(-) originate from the bound excited 3F(0) term of Y(-).

Bauschlicher, Charles W., Jr.↗
NASA NTRS1989

On the electron affinities of the Ca, Sc, Ti and Y atoms

For the Ca, Sc, Ti, and Y atoms calculations are performed for the ground states of the neutrals and the ground and several low-lying excited states of the negative ions. Overall, the computed electron affinities are in good accord with experiment. The calculations show the rapid stabilization of the 3d orbital relative to the 4p as the nuclear charge increases. The 3F0 and 3D0 terms are found to be close in energy in Sc(-) and in Y(-). This confirms earlier speculation that some of the peaks in the photodetachment spectra of Y(-) originate from the bound excited 3F0 term of Y(-).

Bauschlicher, Charles W., Jr.↗
NASA NTRS1975

Line positions of H2O in the 1.33 to 1.45 micron region

Results are presented for an experimental investigation, using a vacuum IR spectrometer, of the line positions and strengths of water vapor in the spectral region from 6900 to 7500 kaysers. The line-center frequencies of the vibration-rotation transitions of the five H2O bands in this spectral interval are determined along with the rotational levels of the (101), (200), (021), (120), and (002) states. It is noted that several of the upper-state levels are perturbed by resonance effects involving either Fermi coupling or Coriolis coupling of the near-resonance levels of various states. Tables are provided which list the measured line-center frequencies, upper- and lower-state rotational quantum numbers, ground-state energy levels, line strengths, and band assignments. It is shown that the (101) and (021) bands are type A with origins at 7249.811 and 6871.51 kaysers, respectively, while the (200), (002), and (120) bands are type B with origins at 7201.540, 7445.07, and 6775.10 kaysers, respectively.

Toth, R. A.↗
NASA NTRS1980

Excitation of the b 3 Sigma u + state of H2 by electron impact - Semiclassical exchange potentials at intermediate energies

Integrated and differential cross sections for the excitation of the b 3 Sigma u + state of H2, from the ground state, by electron impact, are presented. The energy range of interest is 10.5 to 40.0 eV. The close-coupling equations for this process are solved in five different exchange approximations: exact two-electron exchange terms, no orthogonality; exact two-electron exchange terms, orthogonality; semiclassical exchange terms, no orthogonality, with barrier term; semiclassical exchange terms, no orthogonality, no barrier term; and semiclassical exchange terms, orthogonality, with barrier term. The purpose is to judge the reliability of the semiclassical exchange approximation for electronic excitation of molecules by electron impact at intermediate energies. The results are compared with recent theoretical estimates for the same process.

Weatherford, C. A.↗
NASA NTRS1985

Metastability of the midgap level EL 2 in GaAs - Relationship with the As antisite defect

It is found that the rate of the photoinduced transition of the GaAs midgap level EL 2 to its metastable state increases as its occupation increases. High-resolution optical spectra of this transition exhibit a sharp peak very similar to the no-phonon line of the intracenter absorption of the As antisite defect. These findings show that the transition to the metastable state is initiated from the ground state 1A1, and it is finalized via the excited state 1T2 of the neutral As antisite defect. They thus provide a new basis for the critical assessment of the EL 2 metastability models and further confirmation of the association of EL 2 with the isolated As antisite defect.

Skowronski, M.↗
NASA NTRS1998

Bacteriorhodopsin Material and Film Fabrication Issues for Holographic Applications

We discuss issues associated with bacteriorhodopsin (BR) materials and films that affect optical performance in holographic applications. For the D85N variant, some critical parameters include degree of hydration and recording wavelength. The quantum efficiency of the molecular state transition is observed to be apparently dependent on the illumination wavelength. We explain this effect by modeling the photo-activity of the D85N variant as two competing photocycles between the 9-cis and 13-cis retinal configurations. We are able to determine the pure excited P-state absorbance spectrum from the ground state spectrum and mixed population spectra obtained by bleaching to steady-state conditions.

Downie, John D.↗
NASA NTRS2003

High-Velocity Absorption Features in FUSE Spectra of Eta Carinae

Numerous broad (200 to 1000 km/sec) features in the FUSE spectrum (905-1187 A) of eta Carinae are identified as absorption by a forest of high-velocity narrow lines formed in the expanding circumstellar envelope. These features were previously thought to be P-Cygni lines arising in the wind of the central star. The features span a heliocentric velocity range of -140 to -580 km/sec and are seen prominently in low-ionization ground-state transitions (e.g. N I 1134-35, Fe II 1145-42, 1133, 1127- 22, P II 1153, C I 1158) in addition to C III] 1176 A. The high-velocity components of the FUSE transitions have depths about 50% below the continuum. The identifications are consistent with the complex velocity structures seen in ground- and excited-state transitions of Mg I, Mg 11, Fe II, V II, etc observed in STIS/E230H spectra. The origin of other broad features of similar width and depth in the FUSE spectrum, but without low-velocity ISM absorption, are unidentified. However, they are suspected of being absorption of singly-ionized iron-peak elements (e.g. Fe II, V II, Cr II) out of excited levels 1,000 to 20,000 cmE-l above the ground state. The high-velocity features seen in Fe II 1145 are also present in Fe II 1608 (STIS/E140M), but are highly saturated in the latter. Since these transitions have nearly identical log (flambda) (1.998 vs. 2.080), the differences in the profiles are attributable to the different aperture sizes used (30 x 30 arcsec for FUSE, 0.2 x 0.2 arcsec for STIS/E140M). The high-velocity gas appears to be very patchy or has a small covering factor near the central star. Eta Carinae has been observed several times by FUSE over the past three years. The FUSE flux levels and spectral features in eta Car are essentially unchanged over the 2000 March to June 2002 period, establishing a baseline far-UV spectrum in advance of the predicted spectroscopic minimum in 2003.

Sonneborn, G.↗