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At least 55 records · Page 3

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.↗

Spectral absorption coefficients for the fundamental and first overtone vibration-rotation bands of CN

A previous measurement of the transition moment of the fundamental vibration-rotation band of CN is combined with theoretical calculations of relative vibrational transition probabilities in order to compute absorption coefficients for the CN fundamental and first-overtone bands. Line strengths for 121 lines in each branch of all fundamental and first-overtone bands with upper-transition states not greater than 6 are calculated for temperatures of 2000, 3000, and 4000 K; these line strengths are presented as averaged over 8-kayser intervals. The relative vibrational transition moments are placed on an absolute scale, and the wavenumbers of the band origins and heads are given

Bailey, W. L.↗

Atom Resonance Lines for Modeling Atmosphere: Studies of Pressure-Broadening of Alkali Atom Resonance Lines for Modeling Atmospheres of Extrasolar Giant Planets and Brown Dwarfs

We report on progress made in a joint program of theoretical and experimental research to study the line-broadening of alkali atom resonance lines due to collisions with species such as helium and molecular hydrogen. Accurate knowledge of the line profiles of Na and K as a function of temperature and pressure will allow such lines to serve as valuable diagnostics of the atmospheres of brown dwarfs and extra-solar giant planets. A new experimental apparatus has been designed, built and tested over the past year, and we are poised to begin collecting data on the first system of interest, the potassium resonance lines perturbed by collisions with helium. On the theoretical front, calculations of line-broadening due to sodium collisions with helium are nearly complete, using accurate molecular potential energy curves and transition moments just recently computed for this system. In addition we have completed calculations of the three relevant potential energy curves and associated transition moments for K - He, using the MOLPRO quantum chemistry codes. Currently, calculations of the potential surfaces describing K-H2 are in progress.

Hasan, Hashima↗

A theoretical study of the excited states of Ag3

Recently there was considerable interest in the properties and reactivities of small metal clusters. However, for the transition metal trimers, gas phase spectroscopy exists only for Cu3. Calculations are reported for the excited states of the Ag3 molecule. The excitation energies, geometries, derived harmonic frequencies, and transition moments are presented. The electronic structure of these states is very similar to the analogous states of Cu3. From the VCI wave functions transition moments were calculated between each of the Rydberg excited states and the ground state for an equilateral triangle geometry with R sub Ag-Ag = 5.3 a sub 0. One state was computed for the configuration 4d29 5sa sup prime 2 sub 1 5se sup prime 1 sub x 5se sup prime 1 sub y. This configuration was considered since the corresponding configuration for Cu3 is low-lying. Calculations were carried out for a quartet wavefunction in which the 4d hole was localized on the central Ag atom. The spectrum for Ag3 is expected to be simpler than for Cu3 since the 5s2 4d9 states are shifted to higher energy.

Walch, Stephen P.↗

Rotational and vibrational effects in the E 1Sigma(+)g-X 1Sigma(+)g two-photon transitions of H2, HD, and D2

This paper reports a theoretical study of the dependence of the E 1Sigma(+)g v(E) = 0, J-X 1Sigma(+)g, v(X),J transitions in H2, HD, and D2 on the initial vibrational and rotational quantum numbers v(X) and J. The results demonstrate the concerted nature of two-photon transitions. The magnitude of the two-photon transition moment increases with v(X) between 0 and 2, then decreases rapidly at higher v(X). The J dependence of the two-photon transition moment is most strongly affected by the changes in vibrational wave functions caused by centrifugal distortion of the vibrational potential. It is shown that the J variation can be used as a probe of resonant tunneling in the double-well potential of the E,F state.

Huo, Winifred M.↗

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.↗

A model of the Schumann-Runge continuum of O2

Ab initio calculations of the B3Sigma sub u(-) potential energy curve of O2 are reported together with the transition moment connecting the B3Sigma sub u(-) and the ground electronic states. Photodissociation cross sections are presented over the wavelength region 127-152 nm. Small adjustments to the potential energy curve and the transition moment lead to a model of the absorption which agrees well with the experimental cross sections and which reproduces the structural features observed on the high-energy edge. The shoulder at 135.6 nm is attributed to the lowest 3Pi sub u state and the auxiliary maxima to transitions into the B3Sigma sub u(-) state.

Allison, A. C.↗

High-Resolution Electron-Impact Study of the Far-Ultraviolet Emission Spectrum of Molecular Hydrogen

The emission spectrum of molecular hydrogen produced by electron-impact excitation at 100 eV has been measured in the wavelength range 1140-1690 A. High-resolution, optically thin spectra (delta(lambda) = 0.136 A) of the far-ultraviolet (FUV) Lyman and Werner band systems have been obtained with a newly constructed 3 m spectrometer. Synthetic spectral intensities based on the transition probabilities calculated by Abgrall et al. are in very good agreement with experimentally observed intensities. Previous modeling that utilized Allison & Daigarno band transition probabilities with Hoenl-London factors breaks down when the transition moment has significant J dependence or when ro-vibrational coupling is significant. Ro-vibrational perturbation between upsilon = 14 of the B(sup 1)Sigma(sup +, sub u) state and upsilon = 3 of the C(sup 1)Pi(sub u) state and the rotational dependence of the transition moment in the bands of the Lyman system are examined. Complete high-resolution experimental reference FUV spectra, together with the model synthetic spectra based on the Abgrall transition probabilities, are presented. An improved calibration standard is obtained, and an accurate calibration of the 3 m spectrometer has been achieved.

Liu, Xian-Ming↗

Molecular oxygen absorption continua at 195-300 nm and O2 radiative lifetimes

With the aid of new calculations on the transition moments between the six lowest states of O2 (Klotz and Peyerimhoff, 1986), absorption cross sections have been calculated for several oxygen continua. Reasonable agreement is achieved with recent experimental results, the comparison indicating an overestimation of the theoretical transition moment for the A-X system of 20-25 percent. With this adjustment, the calculated radiative lifetime for the O2(A) state is 150 ms, in close agreement with the currently used value. The continua cross sections indicate that absorption by O2(a) cannot be a significant atmospheric process.

Saxon, R. P.↗

Theoretical Study of the Nitric Oxide epsilon and 1100 A Bands

Potential-energy curves, transition-moment functions, Einstein Alpha coefficients and radiative lifetimes associated with the Rydberg state of nitric oxide are calculated in large Gaussian basis sets employing internally contracted MRCI from state-averaged CASSCF wave functions. Computationally, a strong sensitivity of the results to the choice of the CASSCF active space is seen, and careful examination of this behavior gives insight into matters related to the treatment of weakly occupied orbitals, which is a consideration in any study Rydberg excited states. The epsilon system transition-moment function and radiative lifetimes are in disagreement with another calculation in the literature, but reasons for the discrepancies are examined, and the present results are determined to be more accurate.

Sheehy, Jeffrey A.↗

Theoretical study of the NO beta system

A theoretical determination of the transition moment functions (TMFs) for the beta system of NO is presented. High levels of correlation treatment are required to show the changing degree of Rydberg character in the B2II with decreasing r values. The state-averaged complete-active-space self-consistent-field multireference configuration-interaction method is used for the determination. Previous lifetime measurements made with laser-induced fluorescence, varying between 2 and 0.85 microns, are discussed in terms of the calculated lifetimes for v-prime values 0-6, which vary from 2.12-1.17 microns. When larger r values are used for the transition moment function, the calculated lifetimes correlate with experimental lifetimes. The Einstein coefficients agree with experimental results, although limitations in the calibration of the spectrometer can account for systematic differences. The correlation with earlier experimental results suggests that radiative lifetimes are in the range of 1-2 microns.

Langhoff, Stephen R.↗

CMS Token Transition

Within the LHC community, a momentous transition has been occurring in authorization. For nearly 20 years, services within the Worldwide LHC Computing Grid (WLCG) have authorized based on mapping an identity, derived from an X.509 credential, or a group/role, derived from a VOMS extension issued by the experiment. A fundamental shift is occurring to capabilities: the credential, a bearer token, asserts the authorizations of the bearer, not the identity. By the HL-LHC era, the CMS experiment plans for the transition to tokens, based on the WLCG Common JSON Web Token profile, to be complete. Services in the technology architecture include the INDIGO Identity and Access Management server to issue tokens; a HashiCorp Vault server to store and refresh access tokens for users and jobs; a managed token bastion server to push credentials to the HTCondor CredMon service; and HTCondor to maintain valid tokens in long-running batch jobs. We will describe the transition plans of the experiment, current status, configuration of the central authorization server, lessons learned in commissioning token-based access with sites, and operational experience using tokens for both job submissions and file transfers.

43 PARTICLE ACCELERATORS↗

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.↗

Rovibronic molecular line list for the $N_2(C^3Π_u–B^3Π_g)$ second positive system

Here, a line list for the N second positive system, $B^3Π_g—C^3Π_u$, has been compiled using the PGOPHER spectral simulation software. The line list extends the number of vibrational states of the $B^3Π_g$ up to v=29 and a maximum rotational state of J=150 for simulation temperatures up to 7000 K. New electronic–vibrational transition moments were calculated using refined potential energy curves and a transition dipole moment with the DUO software. Comparisons to experimental data and the SPECAIR software have been used to validate the new line list. The results are available in ASCII ExoMol .state and .trans files and as a PGOPHER input file for use in spectral analysis.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Rocket-Plume Spectroscopy Simulation for Hydrocarbon-Fueled Rocket Engines

The UV-Vis spectroscopic system for plume diagnostics monitors rocket engine health by using several analytical tools developed at Stennis Space Center (SSC), including the rocket plume spectroscopy simulation code (RPSSC), to identify and quantify the alloys from the metallic elements observed in engine plumes. Because the hydrocarbon-fueled rocket engine is likely to contain C2, CO, CH, CN, and NO in addition to OH and H2O, the relevant electronic bands of these molecules in the spectral range of 300 to 850 nm in the RPSSC have been included. SSC incorporated several enhancements and modifications to the original line-by-line spectral simulation computer program implemented for plume spectral data analysis and quantification in 1994. These changes made the program applicable to the Space Shuttle Main Engine (SSME) and the Diagnostic Testbed Facility Thruster (DTFT) exhaust plume spectral data. Modifications included updating the molecular and spectral parameters for OH, adding spectral parameter input files optimized for the 10 elements of interest in the spectral range from 320 to 430 nm and linking the output to graphing and analysis packages. Additionally, the ability to handle the non-uniform wavelength interval at which the spectral computations are made was added. This allowed a precise superposition of wavelengths at which the spectral measurements have been made with the wavelengths at which the spectral computations are done by using the line-by-line (LBL) code. To account for hydrocarbon combustion products in the plume, which might interfere with detection and quantification of metallic elements in the spectral region of 300 to 850 nm, the spectroscopic code has been enhanced to include the carbon-based combustion species of C2, CO, and CH. In addition, CN and NO have spectral bands in 300 to 850 nm and, while these molecules are not direct products of hydrocarbon-oxygen combustion systems, they can show up if nitrogen or a nitrogen compound is present as an impurity in the propellants and/or these can form in the boundary layer as a result of interaction of the hot plume with the atmosphere during the ground testing of engines. Ten additional electronic band systems of these five molecules have been included into the code. A comprehensive literature search was conducted to obtain the most accurate values for the molecular and the spectral parameters, including Franck-Cordon factors and electronic transition moments for all ten band systems. For each elemental transition in the RPSSC, six spectral parameters - Doppler broadened line width at half-height, pressure-broadened line width at half-height, electronic multiplicity of the upper state, electronic term energy of the upper state, Einstein transition probability coefficient, and the atomic line center - are required. Input files have been created for ten elements of Ni, Fe, Cr, Co, Cu, Ca, Mn, Al, Ag, and Pd, which retain only relatively moderate to strong transitions in 300 to 430 nm spectral range for each element. The number of transitions in the input files is 68 for Ni; 148 for Fe; 6 for Cr; 87 for Co; 1 for Ca; 3 for Mn; 2 each for Cu, Al, and Ag; and 11 for Pd.

Tejwani, Gopal D.↗

Carbon in Comet Bradfield 1979l

Ultraviolet spectra of comet Bradfield obtained with IUE show a surprising absence of CO(+) despite the presence of CO2(+), and they also show, for the first time, the unambiguous presence of the Mulliken bands of C2. With the use of simultaneous ground-based data, a value of 0.00001 is derived for the transition moment of the a 3 Pi-X 1 Sigma g + transition of C2. The anomalous CO(+)/CO2(+) ratio can be accounted for by the different scale lengths of the species rather than by an abundance difference. Using the model of Feldman (1978), the upper limit for CO(+) is found to be consistent with the observed abundance of CO. On that same model, however, CO cannot produce nearly as much atomic carbon as is observed.

Ahearn, M. F.↗