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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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At least 505 records · Page 28
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

The 2 micron spectrum of NGC 6240 - Evidence for more than a starburst

The exceptionally luminous interacting galaxy NGC 6240 has been studied with infrared spectroscopy and photometry. Emission lines of molecular hydrogen and the Paschen-alpha line of ionized hydrogen have been detected. Broad-band 10 micron and 20 micron emission has also been observed. Combined with previous optical spectroscopy and results from IRAS, the observations show that NGC 6240 cannot be explained along the lines of a superstarburst of massive stars such as seen in M82. It may be more easily understood in terms of an active nucleus similar to Seyfert galaxies.

Depoy, D. L.↗
NASA NTRS2004

Entangled Biphoton Virtual-State Spectroscopy of the A(exp 2)Sigma(sup +)-X(exp 2)Pi System of OH

This Letter describes the first application of entanglement-induced virtual-state spectroscopy to a molecular system. Non-classical, non-monotonic behavior in a two-photon absorption cross section of the OH A-X system, induced by an entangled biphoton state is theoretically demonstrated. A Fourier transform analysis of the biphoton cross section permits access to the energy eigenvalues of intermediate rovibronic states with a fixed excitation photon energy. The dependence of the Fourier spectrum on the tuning range of the entanglement time (T(sub e)) and the relative path delay (tau(sub e)) is discussed. Our analysis reveals that the implementation of molecular virtual-state spectroscopy for the OH A-X system requires the tuning of tau(sub e) over a pico-second range with femto-second resolution.

Kojima, Jun↗
NASA NTRS2004

Entangled Biphoton Virtual-State Spectroscopy of the A(exp 2)Sigma(+) - X(exp 2)Pi System of OH

This Letter describes the first application of entanglement-induced virtual-state spectroscopy to a molecular system. Non-classical, non-monotonic behavior in a two-photon absorption cross section of the OH A-X system, induced by an entangled biphoton state is theoretically demonstrated. A Fourier transform analysis of the biphoton cross section permits access to the energy eigenvalues of intermediate rovibronic states with a fixed excitation photon energy. The dependence of the Fourier spectrum on the tuning range of the entanglement time T(sub e), and the relative path delay tau(sub e) is discussed. Our analysis reveals that the implementation of molecular virtual-state spectroscopy for the OH A-X system requires the tuning of tau(sub e) over a pico-second range with femto-second resolution.

Kojima, Jun↗
DOE OSTI2020

Characterization of light-induced potentials in the strong-field dissociation of O 2 +

In this work, we investigate theoretically the imprints of light-induced potentials (LIPs) on the dissociation dynamics of O 2 + molecular ions, as observable in angle-resolved fragment kinetic-energy-release (KER) spectra. Following the vibrational and rotational dynamics of the initial pump-laser-excited cationic nuclear wave packet, while accounting for the dipole coupling between the O 2 + ( a 4 Π u ) and O 2 + ( f 4 Π g ) electronic states in 800-nm 40-fs probe-laser pulses with peak intensities between 10 13 and 10 14 W / cm 2 , we calculate angle-resolved KER spectra which reveal characteristic energy- and angle-dependent fringe structures. These fringes shift downward in energy as the molecular alignment angle θ relative to the probe-pulse polarization direction increases from 0 to π / 2 . The angle-dependent shifts in the KER fringes increase for larger probe-pulse peak intensities and follow the angle and light-wave-intensity dependence of the vibrational spectrum in the associated Floquet bond-hardening well, which is a manifestation of transient O 2 + nuclear-probability trapping in the LIP during dissociation. By examining the rovibrational dynamics of the dissociating molecular cation near the light-induced conical intersection (LICI) in the cationic LIP surface at θ = π / 2 , we identify related angle-dependent structures in the KER spectra, suggesting a means for assessing the significance of LICIs in molecular dissociation pathways.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Methodology for the development of empirical models relating 13C NMR spectral features to fuel properties

Effective formulation of new gasoline or diesel fuels for internal combustion engines would benefit from the development of reliable models for predicting key fuel properties based on a set of molecular descriptors obtained from a single measurement. This is particularly relevant in the case of renewable fuels, where the available fuel sample quantity may be limited. In this work, we present a statistically-based methodology for building empirical models to predict multiple properties from one-dimensional 13C nuclear magnetic resonance (NMR) spectra measured on around 200 microliters of a liquid fuel. NMR spectra contain information about the molecular composition of a sample and the carbon types and molecular substructures therein. Our approach uses this information to build sparse, interpretable models, where the predicted properties are linked to specific molecular features. The approach takes into consideration the constrained nature of the features making up the one-dimensional NMR spectrum, which, after standardization, represent a relative fuel composition. We point to the limitations in interpretability that arise when building this type of empirical predictive model and suggest how these limitations may be diminished. Among the many properties important for maximizing engine performance and minimizing emissions, we build models that predict derived cetane number and distillation temperatures as these are of particular interest because of their links to fuel economy, drivability, and engine-out emissions. Results suggest that the properties of interest may be impacted by only a few of the 27 13C NMR regions represented in the data, pointing to new directions for further testing in the development of improved fuels.

predictive models, biofuels., NMR Analysis↗
DOE OSTI2024

WFOT: A Wave Function Overlap Tool between Single- and Multi-Reference Electronic Structure Methods for Spectroscopy Simulation

We report the development of a novel diagnostic tool, named wave function overlap tool (WFOT), designed to evaluate the overlap between wave functions computed at single-reference [i.e., time-dependent density functional theory or configuration interaction singles (CIS)] and multireference (i.e., CASSCF/CASPT2) electronic structure levels of theory. It relies on truncating the single- and multireference WFs to CIS-like expansions spanning the same configurational space and maximizing the molecular orbital overlap by means of a unitary transformation. To demonstrate the functionality of the tool, we calculate the transient spectrum of acetylacetone by evaluating excited state absorption signals with multireference quality on top of single-reference on-the-fly dynamics simulations. Semiautomatic spectra generation is facilitated by interfacing the tool with the COBRAMM package, which also allows one to use WFOT with several quantum chemistry codes such as Gaussian, NWChem, and OpenMolcas. Finally, other exciting possibilities for the utilization of the code beyond the simulation of transient absorption spectroscopy are eventually discussed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Preparation of high orbital angular momentum Rydberg states by optical-millimeter-wave STIRAP

Rydberg states of molecules are intrinsically challenging to study due to the presence of fast non-radiative decay pathways, such as predissociation. However, selectively exciting Rydberg states with values of the orbital angular momentum (ℓ) ℓ ≳ 3 is a productive strategy to minimize this rapid decay and to populate molecular Rydberg states with lifetimes that approach those of atoms. Here, in this proof-of-principle demonstration, we transfer population to an nf Rydberg state of the calcium atom by stimulated Raman adiabatic passage, in which an optical and a millimeter-wave field couple the initial and final states via an intermediate nd Rydberg state. Numerical simulations reproduce the observed time and frequency dependences of the population transfer and suggest the utility of this scheme to populate high-ℓ Rydberg states of molecules.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Alpha-relaxation by scattering and medium-range atomic correlation in simple liquids

The relaxation dynamics of liquid and glass can be studied by inelastic x-ray or neutron scattering through the intermediate scattering function F(Q, t), where Q is the momentum transfer of scattering. Because of the time-consuming nature of these measurements, F(Q, t) is usually measured only at the first peak of the structure function S(Q), and its principal decay time is referred to as the α-relaxation time τ α . τ α is generally considered to describe the relaxation time of the bulk, which is related to viscosity and is controlled by the atomic cage around an atom. Here, through simulations on metallic liquids, we show that the α-relaxation time determined by scattering experiments does not purely reflect viscosity but is influenced by changes in spatial cooperativity. We also demonstrate that atomic caging is not exerted by the nearest neighbors but involves more cooperative atomic dynamics of the atomic medium-range order.

Glass transitions↗
DOE OSTI2023

Modeling the sequential dissociative double ionization of O 2 by ultrashort intense infrared laser pulses

A density matrix approach for sequential double ionization (DM-SDI) of molecules has been developed recently and was applied to the N 2 molecule. In this article, we extended the DM-SDI model to O 2 , which is a more complicated system to model than N 2 , due to its electronic structures and spin-orbit and laser couplings in the manifold of doubly charged states. We obtained a good agreement on the kinetic energy release spectrum of O + + O + from previous experiments. Thanks to the low computational cost of the model, we explored the mechanism behind the ionization and dissociation dynamics as well as the effects of lasers on the spectrum. Furthermore, this work will pave the way to model sequential dissociative double ionization of larger molecules and to probe molecular dynamics by measuring kinetic energy release spectra from this process.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2021

Equation-of-Motion Coupled-Cluster Cumulant Green’s Function for Excited States and X-ray Spectra

Green’s function methods within many-body perturbation theory provide a general framework for treating electronic correlations in excited states and spectra. Conventional methods using the Dyson equation or the cumulant expansion are typically based on the GW self-energy approximation. In order to extend this approximation in molecular systems, a non-perturbative real-time coupled-cluster cumulant Green’s function approach has been introduced, where the cumulant is obtained as the solution to a set of coupled first order, non-linear differential equations. This approach naturally includes non-linear corrections to conventional cumulant Green’s function techniques where the cumulant is linear in the GW self-energy. The method yields the spectral function associated with the core Green’s function, which is directly related to the x-ray photoemission spectra (XPS) of molecular systems. The approach also yields very good results for binding energies and satellite excitations. The x-ray absorption spectrum (XAS) is then obtained as a convolution of the core spectral function and an effective one-body absorption spectrum. Here this approach is extended to include the full coupled-cluster-singles (CCS) core Green’s function by including the complete form of the non-linear contributions to the cumulant as well as all single, double, and triple cluster excitations in the CC amplitude equations. This approach naturally builds in orthogonality and shake-up effects analogous to those in the Mahan-Noizeres-de Dominicis edge singularity corrections that enhance the XAS near the edge. Themethod is illustrated for the XPS and XAS of NH 3 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1982

Random walks with the 6420- and 6825-A features of methane: Lost in the wilderness

A feature near 6420 A which appears in the spectra of Uranus and Neptune, and was recently detected in the spectrum of Titan is investigated. When originally identified, it was assigned to the pressure induced 4 to 0 band of molecular hydrogen. Not only did the wavelength agree--a small apparent shift was arm waved away, but when the feature was reduced using a dipole-induced strength, it gave results for H2 column densities consistent with best estimates for the sharp quadrupole lines. In studying the long path spectra of methane, that same feature was also present. A second similar problem exists with a Uranian feature--indeed, a general planetary feature centered near 6825 A.

Lutz, B. L.↗
NASA NTRS1986

Infrared spectra of rotating protostars

Earlier calculations of the infrared emission expected from stars in the process of being made are corrected to include the most important observable effects of rotation and generalized. An improved version of the spherical model of a previous paper is developed, and the corresponding emergent spectral energy distributions are calculated for the theoretically expected mass infall rate in the cores of cool and quiescent molecular clouds. The dust grain opacity model and the temperature profile parameterization are improved. It is shown that the infrared spectrum of the IRAS source 04264+2426, which is associated with a Herbig-Haro object, can be adequately represented in terms of a rotating and accreting protostar. This strengthens the suggestion that collimated outflows in young stellar objects originate when a stellar wind tries to emerge and reverse the swirling pattern of infall which gave birth to the central star.

Adams, F. C.↗
NASA NTRS1995

Hubble Space Telescope FOS spectroscopy of the ultrashort-period dwarf nova WZ Sagittae: The underlying degenerate

Two consecutive Hubble Space Telescope (HST) Faint Object Spectrograph (FOS) spectra of the exposed white dwarf in the ultrashort-period, high-amplitude, dwarf nova WZ Sge, reveal a rich absorption line spectrum of neutron carbon and ionized metals, the Stark-broadened Lyman-alpha absorption wing, the H2 quasi-molecular Lyman-alpha 'satellite' absorption line, and a double-peaked C IV emission line which is variable with orbital phase. A synthetic spectral analysis of the white dwarf yields T(sub eff) = 14,900 K +/- 250 K, log g = 8.0. In order to fit the strongest C I absorption lines and account for the weakness of the silicon absorption lines, the abundance of carbon in the photosphere must be approximately 0.5 solar, silicon abundance is 5 x 10(exp -3) solar, with all other metal species appearing to be 0.1-0.001 times solar. The H2 quasi-molecular absorption is fitted very successfully. The photospheric metals have diffusion timescales of fractions of a year, and thus they must have been accreted long after the 1978 December outburst. The source of the most abundance metal, carbon, is considered. If the time-averaged accretion rate during quiescence is low enough for diffusive equilibrium to prevail, then the equilibrium accretion rate pf neutron carbon is 7 x 10(exp -16) solar mass/yr. A convective dredge-up origin for the concentration of carbon is extremely unlikely, given that the white dwarf atmosphere is H-rich while in single degenerates showing carbon and hydrogen, the C and H are trace elements in a helium background. Additional implications are explored.

Sion, Edward M.↗
NASA NTRS1996

Radioactive Transfer Models for Saturn and Titan

The infrared spectra of the earth's atmosphere and planetary atmospheres contains information about atmospheric physical and chemical processes. Atmospheric molecular constituents absorb and emit infrared radiation by rotational and vibrational transition. Observed spectra exhibit characteristic features in the electromagnetic spectrum region. Observation of the absorption or thermal emission spectra may be obtained with space-borne high resolution infrared spectrometers in the 10-5000 cm(exp -1) (2-1000 micro-m) spectral region. Information about the atmospheric thermal structure, composition, and the chemical and physical processes of the observed spectral was accomplished. A preliminary version of a P-T retrieval algorithm for Saturn using all three modes for temperature inversion, e.g., CH4-limb, and H2-nadir spectra was completed and tested for accuracy. Radiative transfer and inversion programs were studied and analyzed for applications to infrared limb thermal emission observations of Saturn and Titan from the Cassini Orbiter, as well as Earth's atmosphere. Analysis and modification of the existing radiative transfer and inversion programs for Earth and planetary atmospheres are being made. Data analysis and retrieval of information form the observations by digital calculations were carried out at UAH and MSFC computer. The working program for generating and reading g-k arrays for using the c-k arrays via the c-k method for radiative transfer calculations for desired atmospheric and instrumental parameters was completed, tested for accuracy and resides at the MSFC computer.

Wu, S. T.↗
NASA NTRS2000

A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

Hudgins, Douglas M.↗
NASA NTRS1998

Abundances of ethylene oxide and acetaldehyde in hot molecular cloud cores

We have searched for millimetre-wave line emission from ethylene oxide (c-C2H4O) and its structural isomer acetaldehyde (CH3CHO) in 11 molecular clouds using SEST. Ethylene oxide and acetaldehyde were detected through multiple lines in the hot cores NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2. Acetaldehyde was also detected towards G10.47+0.03, G322.2+0.6, and Orion 3'N, and one ethylene oxide line was tentatively detected in G10.47+0.03. Column densities and rotational excitation temperatures were derived using a procedure which fits the observed line intensifies by finding the minimum chi 2-value. The resulting rotational excitation temperatures of ethylene oxide and acetaldehyde are in the range 16-38 K, indicating that these species are excited in the outer, cooler parts of the hot cores or that the excitation is significantly subthermal. For an assumed source size of 20", the deduced column densities are (0.6-1)x10(14) cm-2 for ethylene oxide and (2-5)x10(14) cm-2 for acetaldehyde. The fractional abundances with respect to H2 are X[c-C2H4O]=(2-6)xl0(-10), and X[CH3CHO]=(0.8-3)x10(-9). The ratio X[CH3CHO]/X[c-C2H4O] varies between 2.6 (NGC 6334F) and 8.5 (G327.3-0.6). We also detected and analysed multiple transitions of CH3OH, CH3OCH3, C2H5OH, and HCOOH. The chemical, and possibly evolutionary, states of NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2 seem to be very similar.

Non-NASA Center↗