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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.

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NASA NTRS1986

N(+)-N and O(+)-O interaction energies, dipole transition moments, and transport cross sections

Complete sets of ion-atom interaction energies have been computed for nitrogen and oxygen with accurate large scale structure calculations. The computed energies agree well with the accurate potential curves available from spectroscopic measurement. The state functions from the nitrogen calculations have been applied to determine the transition moment for all allowed dipole transitions. These results can be combined to compute a detailed radiation spectrum such as that required to define the highly nonequilibrium environment of aeroassisted orbital transfer vehicle (AOTV). The long-range interaction energies have been used to determine the ion-atom resonance charge exchange cross sections that are important for transport processes such as diffusion. A calculation to determine reliable transport properties for energies that include the AOTV temperature range from these computed properties is described.

Partridge, H.↗

NASA NTRS1986

Dipole moments and transition probabilities of the a 3Sigma(+)g - b 3Sigma(+)u system of molecular hydrogen

Multiconfiguration variational calculations of the electronic wave functions of the a 3Sigma(+)g and b 3Sigma(+)u states of molecular hydrogen are presented, and the electric dipole transition moment between them (of interest in connection with stellar atmospheres and the UV spectrum of the Jovian planets) is obtained. The dipole moment is used to calculate the probabilities of radiative transitions from the discrete vibrational levels of the a 3Sigma(+)g state to the vibrational continuum of the repulsive b 3Sigma(+)u state as functions of the wavelength of the emitted photons. The total transition probabilities and radiative lifetimes of the levels v prime = 0-20 are presented.

Guberman, S.↗

NASA NTRS1978

Semirigorous bounds for the dipole moments and transition moments of the LiH molecule

Semirigorous error limits for the dipole moments and transition moments of LiH at R = 3.015 bohr are reported. Weinhold's formula for the upper and lower bounds to transition moments is extended to include transitions between states of the same symmetry, and Chong's (1976) semirigorous expression for the lower bound to the overlap between the approximate and the true wavefunctions is applied to the calculation. The semirigorous theory of Chong was also generalized in the sense that the zeroth-order wavefunction was allowed to contain many configuration state functions instead of just the Hartree-Fock or first natural configuration state function.

Langhoff, S. R.↗

NASA NTRS1988

Core-core and core-valence correlation

The effect of 1s core correlation on properties and energy separations are analyzed using full configuration-interaction (FCI) calculations. The Be1S - 1P, the C 3P - 5S,m and CH(+) 1Sigma(+) - 1Pi separations, and CH(+) spectroscopic constants, dipole moment, and 1Sigma(+) - 1Pi transition dipole moment have been studied. The results of the FCI calculations are compared to those obtained using approximate methods.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1979

On nuclear spin statistics in rotational transition intensities in tetrahedral AB4 molecules

A general expression is derived for the integrated intensity of rotational transitions in the vibronic ground state of tetrahedral molecules, taking into account the nuclear spin statistics. It is shown that the ratio of this expression to previously published spin-free integrated intensities depends only on the tensor character N of the operator driving the transition, the appropriate rotational quantum numbers J and J', and the nuclear spin of the identical nuclei. Tables are given for N = 3, 4 and J no more than 50, which enable the calculation of integrated intensities for octopole and hexadecapole collision-induced dipole-moment transitions, centrifugal-distortion-induced dipole-moment transitions, and centrifugal-distortion-induced anisotropic-polarizability-tensor Raman transitions.

Rosenberg, A.↗

NASA NTRS1988

Core-core and core-valence correlation

The effect of (1s) core correlation on properties and energy separations was analyzed using full configuration-interaction (FCI) calculations. The Be 1 S - 1 P, the C 3 P - 5 S and CH+ 1 Sigma + or - 1 Pi separations, and CH+ spectroscopic constants, dipole moment and 1 Sigma + - 1 Pi transition dipole moment were studied. The results of the FCI calculations are compared to those obtained using approximate methods. In addition, the generation of atomic natural orbital (ANO) basis sets, as a method for contracting a primitive basis set for both valence and core correlation, is discussed. When both core-core and core-valence correlation are included in the calculation, no suitable truncated CI approach consistently reproduces the FCI, and contraction of the basis set is very difficult. If the (nearly constant) core-core correlation is eliminated, and only the core-valence correlation is included, CASSCF/MRCI approached reproduce the FCI results and basis set contraction is significantly easier.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1992

Dipole moments and transition probabilities of the i 3Pi sub g-b 3Sigma(+) sub u, c 3Pi sub u-a 3Sigma(+) sub g, and i 3Pi sub g-c 3Pi sub u systems of molecular hydrogen

Bonn-Oppenheimer-based ab initio calculations of dipole moments from the i 3Pi sub g-b 3Sigma(+) sub u, c 3Pi sub u-a 3Sigma(+) sub g, and i 3Pi sub g-c 3Pi sub u transitions of H2 have been conducted, to yield a tabulation of the dipole transition probabilities and Franck-Condon factors. These factors are given for transitions originating in the lowest vibrational level of the ground X 1Sigma(+) sub g state.

Guberman, Steven L.↗

NASA NTRS2006

Computational Spectroscopy of Polycyclic Aromatic Hydrocarbons In Support of Laboratory Astrophysics

Polycyclic aromatic hydrocarbons (PAHs) are strong candidates for the molecular carriers of the unidentified infrared bands (UIR) and the diffuse interstellar bands (DIBs). In order to test the PAH hypothesis, we have systematically measured the vibronic spectra of a number of jet-cooled neutral and ionized PAHs in the near ultraviolet (UV) to visible spectral ranges using the cavity ring-down spectroscopy. To support this experimental effort, we have carried out theoretical studies of the spectra obtained in our measurements. Ab initio and (time-dependent) density.functiona1 theory calculations are performed to obtain the geometries, energetics, vibrational frequencies, transition dipole moments, and normal coordinates of these PAH molecules. Franck-Condon (FC) calculations and/or vibronic calculations are then performed using the calculated normal coordinates and vibrational frequencies to simulate the vibronic spectra. It is found that vibronic interactions in these conjugated pi electron systems are often strong enough to cause significant deviations from the Born-Oppenheimer (BO) approximation. For vibronic transitions that are well described by the BO approximation, the vibronic band profiles are simulated by calculating the rotational structure of the vibronic transitions. Vibronic oscillator strength factors are calculated in the frame of the FC approximation from the electronic transition dipole moments and the FC factors. This computational effort together with our experimental measurements provides, for the first time, powerful tools for comparison with space-based data and, hence, a powerful approach to understand the spectroscopy of interstellar PAH analogs and the nature of the UIR and DIBs.

Tan, Xiaofeng↗

NASA NTRS2025

Line List for the A 2 Π−X 2 Σ + and the B 2 Σ + −X 2 Σ + Band Systems of CaF

The spectral analysis of molecule-rich asymptotic giant branch (AGB) stars is challenging. Although other calcium and fluorine bearing molecules are observed in the microwave and in the visible spectrum of AGB stars, CaF has never been detected, despite favorable chemical equilibrium predictions. Yet, measuring the CaF abundance could give more insight into the fluorine budget of AGB stars and allow better simulation of stellar spectra. In this work, we present an analysis of the visible spectrum of CaF obtained with a Fourier transform spectrometer. CaF A 2 Π−X 2 Σ + and the B 2 Σ + −X 2 Σ + band systems were excited with a hollow cathode discharge. Using previous fluorescence spectroscopy measurements, highly accurate ground state constants, and reasonable extrapolation schemes, the strongest features of CaF in the visible spectrum can be accurately modeled for both band systems. Spectroscopic constants are determined for A 2 Π with v ≤ 16 and for B 2 Σ + with v ≤ 20. Ab initio transition dipole moment curves of both transitions were calculated and scaled, and we provide a line list with Einstein A coefficients and oscillator strengths. This line list can be used to simulate spectra of CaF at temperatures and pressures relevant to astrophysical environments.

Léo Lavy↗

NASA NTRS1982

Microwave rotational spectroscopy

The region of planetary atmospheres upward of 1 millimeter is considered. The applications of this region, how microwave, millimeter, and submillimeter spectra (the so called rotational spectra) can fruitfully interact with infrared spectral measurements are described. Both the rotational bands and vibrational bands of molecules are considered. A typical rotational absorption coefficient for a linear molecule in a low J state with a dipole moment of about one Debye is plotted and evaluated. A vibrational case was chosen similarly: the transition dipole moment used for the vibrational case is typical of CO at the peak of its rotational distribution. Information on high altitude parameters that often cannot be obtained from higher frequency spectra, which can be provided by rotational spectra is discussed.

Pickett, H.↗

NASA NTRS1983

The low-lying 2-sigma-minus states of OH

The configuration-interaction method is used to determine the electronic wave functions of the two lowest 2-sigma-minus states of OH using four different atomic orbital basis sets. Potential energy curves, transition moments, oscillator strengths, and photodissociation cross sections are obtained. Electronic transition dipole moments connecting the excited 1 2-sigma-minus and 2(D)2-sigma-minus states with each other and with the ground chi-2-pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D-2-sigma-minus(v prime = 0) from chi-2-pi(v double prime = 0) transition are in good agreement with the empirical value derived from astronomical measurement. The photodissociation cross sections for absorption from the v prime = 0, 1, and 2 levels of the ground state into the continuum of the 1 2-sigma-minus state are calculated, and the interstellar and cometary photodissociation rates are derived.

Van Dishoeck, E. F.↗

NASA NTRS1982

Radiative lifetimes and dipole moments of the A 2Sigma/+/, B 2Sigma /+/, and C 2Sigma/+/ states of OH

After describing independent theoretical studies of the eigenfunctions of the X 2Pi and excited A 2Sigma(+), B 2Sigma(+), and C 2Sigma(+) states of OH, results are presented for the transition dipole moments connecting each excited state to the others and to the ground state. The radiative lifetimes derived from calculation of the bound-bound and bound-free vibrational band transition probabilities are compared with measured values, confirming recent measurements of the A 2Sigma(+) and C 2Sigma(+) states but not the lifetimes measured for the B 2Sigma(+) state.

Langhoff, S. R.↗

NASA NTRS1988

Molecular processes in comets

The transition dipole moments of the c 3 Pi u - a 3 Sigma g +, i 3 Pi g - c 3 Pi u, and i 3 Pi g - b 3 Sigma u + transitions of molecular hydrogen were calculated over a wide range of internuclear distances R. Calculations of the emission spectra are nearing completion. Substantial progress was made in the calculation of the absorption coefficient of a colliding pair of hydrogen atoms in the binary encounter approximation. Detailed calculations were performed on the continuum emission arising from the excitation of the a 3 sigma g + state of H2 by the impact of electrons of various energies. Each curve is labelled by the electron energy in electron volts. The strong emission near Lyman alpha is interesting in that it is produced by excitation of molecular hydrogen.

Dalgarno, A.↗

NASA NTRS1985

Transition probabilities of the B-prime 1Sigma(u)(+) to X 1Sigma(g)(+) system of molecular hydrogen

From published potential energy curves and transition dipole moments, there are obtained by numerical integration of the equations of nuclear motion the vibrational eigenfunctions of the X 1Sigma(g)(+) and B-prime 1Sigma(u)(+) states of H2. The probabilities of radiative transitions from the discrete vibrational levels of the excited B-prime 1Sigma(u)(+) electronic state of H2 to the discrete and continuum vibrational levels of the ground X 1Sigma(g)(+) electronic state are calculated. The Franck-Condon factors are also presented.

Kwok, T. L.↗

NASA NTRS1995

Theoretical Study of the B(sup 3) Sigma(sup -, sub u) - X(sup3)Sigma(sub g, sup -) and B"(sup 3)Pi(sub u) - X(sup 3)Sigma(sub g, sup -) Band Systems of S(sub 2)

Multireference configuration-interaction (MRCI) wavefunctions and potential energy curves have been calculated for the X(sup 3)Sigma(sub g,sup -), B(sup 3)Sigma(sub u, Sup -) and B"(sup 3)Pi((sub u) states of S(sub 2) using correlation consistent Gaussian basis sets. These wavefunctions are utilized to compute the the transition dipole moments of the B(sup 3)Sigma(sub g, sup -) - X(sup 3) Sigma(sub g, sup -) and B"(sup 3)Pi(sub u) - X(sup 3)Sigma(sub g, sup -) systems. Oscillator strengths, transition probabilities, and radiative lifetimes are computed for the X-B system and comparison is made with experimental data.

Pradhan, Atul D.↗

NASA NTRS1986

An interstellar line coincident with the P(2,1) transition of hydronium (H3O+)

Double-sideband observations of the Orion KL nebular region with the NRAO 12 m radiotelescope in March 1986 detected a weak emission spectral line that coincided with the P(2,1) rotation-inversion transition of H3O+. Spectral maps are provided for the observed line at 307,192 MHz with 2 and 1 MHz resolution. The line parameters, along with a calculated transition dipole moment of 1.44 D, are used to estimate column densities of 7.7 and 8.7 x 10 to the 13/sq cm for excitation temperatures of 50 and 90 K, respectively. A minimum H2 density of 1 million/cu cm is estimated for the region if the thermalization of the transition to the excitation temperatures is to occur. Finally, fractional abundances of H2O in the Orion cloud are projected to be 1/100,000 and 1/1 million for the nonthermal and thermal transition cases, respectively.

Hollis, J. M.↗

NASA NTRS1982

Molecular processes in comets

Potential energy curves for the two lowest 2 sigma- states of OH are computed at the configuration-interaction level using four different basis sets. Electronic transition dipole moments connecting the excited 1 2 sigma- and 2(D) 2 sigma- states with each other and with he ground X2pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D 2 sigma-(v prime=0) reverser to X 2pi (v prime prime=0) transition are in good agreement with the empirical value derived from astronomical measurements. The photodissociation cross sections for absorption rom the v prime prime=0,1, and levels of the ground state into the continuum of the 1 2 sigma- state are calculated, and the interstellar and cometary photodissociation rates are derived.

Dalgarno, A.↗

NASA NTRS1983

Theoretical study of NH2 - Potential curves, transition moments, and photodissociation cross sections

Photodissociation cross sections from the ground state of NH2 have been calculated using a pseudodiatomic model. The potential curves needed in these calculations, functions of one NH bond length, were obtained by ab initio MCSCF calculations on the five lowest doublet states of NH2 using a contracted Gaussian basis set of double zeta quality augmented by polarization and Rydberg functions. Transition dipole moments between the ground and excited states were evaluated using MCSCF wave functions.

Saxon, R. P.↗