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At least 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

The ezSpectra suite: An easy‐to‐use toolkit for spectroscopy modeling

Abstract A molecule's spectrum encodes information about its structure and electronic properties. It is a unique fingerprint that can serve as a molecular ID. Quantum chemistry calculations provide key ingredients for interpreting spectra, but modeling the spectra rarely ends there; it requires additional steps that entail combined treatments of electronic and nuclear degrees of freedom and account for specifics of the experimental setup (light energy, polarization, averaging over molecular orientations, temperature, etc.). This Software Focus article describes the ezSpectra suite, which currently comprises two stand‐alone open‐source codes: ezFCF and ezDyson . ezFCF calculates Franck–Condon factors, which yield vibrational progressions for polyatomic molecules, within the double‐harmonic approximation. ezDyson calculates absolute cross‐sections for photodetachment/photoionization processes and photoelectron angular distributions using Dyson orbitals computed by a quantum chemistry program. This article is categorized under: Electronic Structure Theory > Ab Initio Electronic Structure Methods Theoretical and Physical Chemistry > Spectroscopy Software > Simulation Methods

Gozem, Samer↗
DOE OSTI2024

The interplay of excitonic delocalization and vibrational localization in optical lineshapes: A variational polaron approach

The dynamics of molecular excitonic systems are complicated by a competition between electronic coupling (which drives delocalization) and vibrational-electronic (vibronic) interactions (which tend to encourage electronic localization). A particular challenge of molecular systems is that they typically possess a large number of independent vibrations, with frequencies often spanning the entire spectrum of relevant electronic energy gaps. Recent spectroscopic observations and numerical simulations on a water-soluble chlorophyll-binding protein (WSCP) reveal a transition between two regimes of vibronic behavior, a Redfield-like regime in which low-frequency vibrations respond to a delocalized excitonic state, and a Förster-like regime where high-frequency vibrations act as incoherent excitations on individual pigments. Although numerical simulations can reproduce these effects, there is a need for a simple, systematic theory that accurately describes the smooth transition between these two regimes in experimental spectra. Here we address this challenge by generalizing the variational polaron transform approach of [Bloemsma et al., Chem. Phys. 481, 250 (2016)] to include arbitrary bath densities for systems with or without symmetry. We benchmark this theory against both numerical matrix-diagonalization methods and experimental 77 K fluorescence spectra for two WSCP variants, obtaining quite satisfactory agreement in both cases. Here, we apply this theory to offer an explanation for the large loss in apparent electronic coupling in the WSCP Q57K mutant and to examine the likely impact of the interplay between excitonic delocalization and vibrational localization on vibrational sideband shapes and apparent coupling strengths in high-resolution optical spectra for chlorophyll-protein complexes such as WSCP.

14 SOLAR ENERGY↗
DOE OSTI2020

Electrogenerated Chemiluminescence of Near-Infrared-Emitting CdSe@CdSe Nanorods in Aqueous Solution

Electrogenerated chemiluminescence (ECL) was observed from TOPO-capped CdSe@CdSe nanorods (NRs) depositing on a metal electrode in phosphate buffer solution (PBS). Two ECL peaks at -1.05 and -1.33 V in pH 9.2, 0.1 M PBS were found under cyclic voltammetric conditions. Cyclic voltammetry of this solution displayed no distinctive features, on the other hand, light emission was observed during cyclic potential scans. Additionally, the photoluminescence (PL) spectrum showed an emission maximum at 692 nm. The spectrum of ECL possesses one peak which coincides very well with the PL spectrum of the nanorods film. The mechanism for ECL peaks was proposed. Electron transfer reactions between charged nanorods and molecular redox-active coreactants such as dissolved oxygen and H2O2 or between positively and negatively charged nanorods occurred that led to electron and hole annihilation, producing light.

36 MATERIALS SCIENCE↗
NASA NTRS1969

Laser radar measurements of the aerosol content of the atmosphere

A summary of the results of laser radar observations of atmospheric aerosols is presented along with a description of the laser radar system devised during the study and of the data handling techniques utilized for the analysis of the data of the temporal and spatial distribution of atmospheric aerosols. Current research conducted by the group is directed toward the analysis of the frequency spectrum of laser radar echoes to obtain absolute measurements of the dust content of the atmosphere by resolving the molecular and aerosol contributions to the laser radar echoes.

Grams, G. W.↗
NASA NTRS1972

Infrared spectra of molecules and materials of astrophysical interest

Vibrational spectra were studied from 400 to 33/cm for molecules which may be present in the atmosphere of Jovian planets. The microwave spectrum of cis glyoxal was studied. Sources of color variation in the Jovian atmosphere were analyzed in relation to molecular crystals. The low frequency modes of acetaldehyde and acetaldehyde-d sub 4 are discussed.

Durig, J. R.↗
NASA NTRS1988

Infrared radiative transfer in dense disks around young stars

A two-dimensional radiative transfer program has been used to determine the temperature distribution within cylindrically symmetric, centrally heated dust clouds. In particular, the disk-shaped structures observed around young luminous stars have been modeled. Changing the dust distribution in these disks primarily affected the observed morphology in the near-infrared and far-infrared, and at millimeter wavelengths. The overall cloud spectrum, however, was mainly determined by the characteristics of the grains themselves. Comparison with published far-infrared and molecular line data has indicated that the dust density can generally be modeled by a power-law distribution in r with index of -2 and an exponential in z with disk thickness proportional to 1/r. When observed nearly edge-on, scattered direct stellar radiation is observed in the polar regions in the form of comet-shaped lobes of emission.

Dent, William R. F.↗
NASA NTRS1996

Variations in the 3 Micron Spectrum Across the Orion Bar: PAHS and Related Molecules

Long-slit spectra across the Orion Bar reveal significant differences in the spatial behavior of the components of the 3 micrometer PAH spectrum. The strong PAH band at 3.29 micrometers generally decreases exponentially with distance from the ionization front into the molecular cloud (scale height approximately 12"), although excesses appear approximately 10" and approximately 20" behind the ionization front, close to layers of H2 and CO emission respectively. The 3.40 micrometer PAH feature separates into two components with very different spatial distributions. The main component (at 3.395 micrometers), along with the 3.51 micrometer band and the PAH plateau (3.3-3.6 micrometers), shows excess emission approximately 10" and approximately 20" behind the ionization front, stronger than the excesses in the 3.29 micrometer band. The extra component of the 3.40 micrometer band, which peaks at approximately 3.405 micrometers, has a spatial distribution very similar to the H2 emission. Aromatic C-H stretches in PAHs most likely produce the 3.29 micrometer feature. Aliphatic C-H stretches in either attached methyl sidegroups or super-hydrogenated PAHs (H-PAHs), or perhaps both, could produce the complicated spectral and spatial structure at 3.40 micrometers. The distribution of these fragile PAH-based species traces the physical and chemical conditions in the interface between the ionized region and molecular cloud.

Sloan, G. C.↗
NASA NTRS1997

Variations in the 3 micron spectrum across the Orion Bar: polycyclic aromatic hydrocarbons and related molecules

Long-slit spectra across the Orion Bar reveal significant differences in the spatial behavior of the components of the 3 microns polycyclic aromatic hydrocarbon (PAH) spectrum. The strong PAH band at 3.29 microns generally decreases exponentially with distance from the ionization front into the molecular cloud (scale height approximately 12"), although excesses appear approximately 10" and 20" behind the ionization front, close to layers of H2 and CO emission, respectively. The 3.40 microns PAH feature separates into two components with very different spatial distributions. The main component (at 3.395 microns), along with the 3.51 microns band and the PAH plateau (3.3-3.6 microns), shows excess emission approximately 10" and approximately 20" behind the ionization front, stronger than the excesses in the 3.29 microns band. The extra component of the 3.40 microns band, which peaks at approximately 3.405 microns, has a spatial distribution very similar to the H2 emission. Aromatic C-H stretches in PAHs most likely produce the 3.29 microns feature. Aliphatic C-H stretches in either attached methyl side-groups or superhydrogenated PAHs, or perhaps both, could produce the complicated spectral and spatial structure at 3.40 microns.

NASA Center ARC↗
NASA NTRS1991

Development of a Nonequilibrium Radiative Heating Prediction Method for Coupled Flowfield Solutions

A method for predicting radiative heating and coupling effects in nonequilibrium flow-fields has been developed. The method resolves atomic lines with a minimum number of spectral points, and treats molecular radiation using the smeared band approximation. To further minimize computational time, the calculation is performed on an optimized spectrum, which is computed for each flow condition to enhance spectral resolution. Additional time savings are obtained by performing the radiation calculation on a subgrid optimally selected for accuracy. Representative results from the new method are compared to previous work to demonstrate that the speedup does not cause a loss of accuracy and is sufficient to make coupled solutions practical. The method is found to be a useful tool for studies of nonequilibrium flows.

Hartung, Lin C.↗
NASA NTRS2012

Solar Cell Short Circuit Current Errors and Uncertainties During High Altitude Calibrations

High altitude balloon based facilities can make solar cell calibration measurements above 99.5% of the atmosphere to use for adjusting laboratory solar simulators. While close to on-orbit illumination, the small attenuation to the spectra may result in under measurements of solar cell parameters. Variations of stratospheric weather, may produce flight-to-flight measurement variations. To support the NSCAP effort, this work quantifies some of the effects on solar cell short circuit current (Isc) measurements on triple junction sub-cells. This work looks at several types of high altitude methods, direct high altitude meas urements near 120 kft, and lower stratospheric Langley plots from aircraft. It also looks at Langley extrapolation from altitudes above most of the ozone, for potential small balloon payloads. A convolution of the sub-cell spectral response with the standard solar spectrum modified by several absorption processes is used to determine the relative change from AMO, lscllsc(AMO). Rayleigh scattering, molecular scatterin g from uniformly mixed gases, Ozone, and water vapor, are included in this analysis. A range of atmosph eric pressures are examined, from 0. 05 to 0.25 Atm to cover the range of atmospheric altitudes where solar cell calibrations a reperformed. Generally these errors and uncertainties are less than 0.2%

Snyder, David D.↗
DOE OSTI2022

A localized view on molecular dissociation via electron-ion partial covariance

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d 3/2 and 4d 5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Kβ X-ray Emission Spectroscopy of Cu(I)-Lytic Polysaccharide Monooxygenase: Direct Observation of the Frontier Molecular Orbital for H 2 O 2 Activation

Lytic polysaccharide monooxygenases (LPMOs) catalyze the degradation of recalcitrant carbohydrate polysaccharide substrates. These enzymes are characterized by a mononuclear Cu(I) active site with a three-coordinate T-shaped “His-brace” configuration including the N-terminal histidine and its amine group as ligands. Here, this study explicitly investigates the electronic structure of the d 10 Cu(I) active site in a LPMO using Kβ X-ray emission spectroscopy (XES). The lack of inversion symmetry in the His-brace site enables the 3d/p mixing required for intensity in the Kβ valence-to-core (VtC) XES spectrum of Cu(I)-LPMO. These Kβ XES data are correlated to density functional theory (DFT) calculations to define the bonding, and in particular, the frontier molecular orbital (FMO) of the Cu(I) site. These experimentally validated DFT calculations are used to evaluate the reaction coordinate for homolytic cleavage of the H 2 O 2 O–O bond and understand the contribution of this FMO to the low barrier of this reaction and how the geometric and electronic structure of the Cu(I)-LPMO site is activated for rapid reactivity with H 2 O 2 .

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Neutron scattering and neural-network quantum molecular dynamics investigation of the vibrations of ammonia along the solid-to-liquid transition

Abstract Vibrational spectroscopy allows us to understand complex physical and chemical interactions of molecular crystals and liquids such as ammonia, which has recently emerged as a strong hydrogen fuel candidate to support a sustainable society. We report inelastic neutron scattering measurement of vibrational properties of ammonia along the solid-to-liquid phase transition with high enough resolution for direct comparisons to ab-initio simulations. Theoretical analysis reveals the essential role of nuclear quantum effects (NQEs) for correctly describing the intermolecular spectrum as well as high energy intramolecular N-H stretching modes. This is achieved by training neural network models using ab-initio path-integral molecular dynamics (PIMD) simulations, thereby encompassing large spatiotemporal trajectories required to resolve low energy dynamics while retaining NQEs. Our results not only establish the role of NQEs in ammonia but also provide general computational frameworks to study complex molecular systems with NQEs.

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

Photoionization of the I 4d and valence orbitals of methyl iodide

Here, the photoabsorption and photoionization dynamics of the I 4d and valence orbitals in methyl iodide have been studied both experimentally and theoretically. Synchrotron radiation has been employed to measure the total ion yield in the vicinity of the I 4d ionization thresholds. The observed structure, due to excitations into Rydberg or valence states, has been assigned using transition energies and relative intensities computed with time-dependent density functional theory within the Tamm–Dancoff approximation. Photoelectron spectra, recorded with plane polarized radiation in two polarization geometries, have allowed the effect of autoionization on the valence electron angular distributions to be investigated. The spectra obtained at photon energies of 50.62 and 52.34 eV, coinciding respectively with the I 4d 5/2 → σ* and 4d 3/2 → σ* transitions, reveal, in addition to valence shell photoelectron bands, features not associated with simple photoionization of the parent molecule. High resolution photoelectron spectra of the I 4d main-lines display structure resulting from spin–orbit coupling and molecular field splitting. The binding energies of the five states contributing to the (I 4d) -1 ionization have been determined. The iodine (in CH 3 I) N 45 VV Auger spectrum has been measured and the observed structure has been assigned using the core hole binding energies derived in the present work together with established ionization energies of the doubly charged ion. The experimentally determined Auger electron angular distributions have been discussed in relation to the theoretical angular distribution parameter characterizing the spatial alignment of molecular axes in the (I 4d) -1 state.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1994

Flat spectrum T Tauri stars: The case for infall

We show that the mid- to far-infrared fluxes of 'flat spectrum' T Tauri stars can be explained by radiative equilibrium emission from infalling dusty envelopes. Infall eliminates the need for accretion disks with non-standard temperature distributions. The simplicity and power of this explanantion indicates that models employing 'active' disks, in which the temperature distribution is a parameterized power law, should be invoked with caution. Infall also naturally explains the scattered light nebulae detected around many flat spectrum sources. To match the observed spectra, material must fall onto a disk rather than the central star, as expected for collapse of a rotating molecular cloud. It may be necessary to invoke cavities in the envelopes to explain the strength of optical and near-infrared emission; these cavities could be produced by the powerful bipolar outflows commonly observed from young stars. If viewed along the cavity, a source may be lightly extincted at visual wavelengths, while still accreting substantial amounts of material from the envelope. Infall may also be needed to explain the infrared-bright companions of many optical T Tauri stars. This picture suggests that many of the flat spectrum sources are 'protostars'-young stellar objects surrounded by dust infalling envelopes of substantial mass.

Calvet, Nuria↗
NASA NTRS2002

Spectroscopic Detection of a Stellar-like Photosphere in an Accreting Protostar

We present high-resolution (R is approximately equal to 18,000), high signal-to-noise 2 micron spectra of two luminous, X-ray flaring Class I protostars in the rho Ophiuchi cloud acquired with the NIRSPEC (near infrared spectrograph) of the Keck II telescope. We present the first spectrum of a highly veiled, strongly accreting protostar which shows photospheric absorption features and demonstrates the stellar nature of its central core. We find the spectrum of the luminous (L (sub bol) = 10 solar luminosity) protostellar source, YLW 15, to be stellar-like with numerous atomic and molecular absorption features, indicative of a K5 IV/V spectral type and a continuum veiling r(sub k) = 3.0. Its derived stellar luminosity (3 stellar luminosity) and stellar radius (3.1 solar radius) are consistent with those of a 0.5 solar mass pre-main-sequence star. However, 70% of its bolometric luminosity is due to mass accretion, whose rate we estimate to be 1.7 x 10(exp -6) solar masses yr(exp -1). We determine that excess infrared emission produced by the circumstellar accretion disk, the inner infalling envelope, and accretion shocks at the surface of the stellar core of YLW 15 all contribute significantly to its near-IR (infrared) continuum veiling. Its rotational velocity v sin i = 50 km s(exp -1) is comparable to those of flat-spectrum protostars but considerably higher than those of classical T Tauri stars in the rho Oph cloud. The protostar may be magnetically coupled to its circumstellar disk at a radius of 2 - 3 R(sub *). It is also plausible that this protostar can shed over half its angular momentum and evolve into a more slowly rotating classical T Tauri star by remaining coupled to its circumstellar disk (at increasing radius) as its accretion rate drops by an order of magnitude during the rapid transition between the Class I and Class II phases of evolution. The spectrum of WL 6 does not show any photospheric absorption features, and we estimate that its continuum veiling is r(sub k) is greater than or equal to 4.6. Its low luminosity (2 solar masses) and high veiling dictate that its central protostar is very low mass, M is approx. 0.1 solar masses. We also evaluate multi-epoch X ray data along with these spectra and conclude that the X ray variabilities of these sources are not directly related to their protostellar rotation velocities.

Greene, Thomas P.↗
NASA NTRS2008

Eta Carinae across the 2003.5 Minimum: Analysis in the Visible and Near Infrared Spectral Region

We present analysis of the visible through near infrared spectrum of eta Car and its ejecta obtained during the 'eta Car Campaign with the Ultraviolet Visual Echelle Spectrograph (UVES) at the ESO Very Large Telescope (VLT)'. This is a part of larger effort to present a complete eta Car spectrum, and extends the previously presented analyses with the Hubble Space Telescope/Space Telescope Imaging Spectrograph (HST/STIS) in the UV (1240-3159 A) to 10,430 A. The spectrum in the mid and near UV is characterized by the ejecta absorption. At longer wavelengths, stellar wind features from the central source and narrow emission lines from the Weigelt condensations dominate the spectrum. However, narrow absorption lines from the circumstellar shells are present. This paper provides a description of the spectrum between 3060 and 10,430 A, including line identifications of the ejecta absorption spectrum, the emission spectrum from the Weigelt condensations and the P-Cygni stellar wind features. The high spectral resolving power of VLT/UVES enables equivalent width measurements of atomic and molecular absorption lines for elements with no transitions at the shorter wavelengths. However, the ground based seeing and contributions of nebular scattered radiation prevent direct comparison of measured equivalent widths in the VLT/UVES and HST/STIS spectra. Fortunately, HST/STIS and VLT/UVES have a small overlap in wavelength coverage which allows us to compare and adjust for the difference in scattered radiation entering the instruments apertures. This paper provide a complete online VLT/UVES spectrum with line identifications and a spectral comparison between HST/STIS and VLT/UVES between 3060 and 3160 A.

Nielsen, K. E.↗
NASA NTRS2009

Eta Carinae across the 2003.5 Minimum: Analysis in the Visible and Near Infrared Spectral Region

We present an analysis of the visible through near infrared spectrum of Eta Car and its ejecta obtained during the "Eta Car Campaign with the Ultraviolet and Visual Echelle Spectrograph (UVES) at the ESO Very Large Telescope (VLT)". This is a part of the larger effort to present a complete Eta Car spectrum, and extends the previously presented analyses with the Hubble Space Telescope/Space Telescope Imaging Spectrograph (HST/STIS) in the UV (1240-3159 Angstrom) to 10,430 Angstrom. The spectrum in the mid and near UV is characterized by the ejecta absorption. At longer wavelengths, stellar wind features from the central source and narrow emission lines from the Weigelt condensations dominate the spectrum. However, narrow absorption lines from the circumstellar shells are present. This paper provides a description of the spectrum between 3060 and 10,430 Angstroms, including line identifications of the ejecta absorption spectrum, the emission spectrum from the Weigelt condensations and the P-Cygni stellar wind features. The high spectral resolving power of VLT/UVES enables equivalent width measurements of atomic and molecular absorption lines for elements with no transitions at the shorter wavelengths. However, the ground based seeing and contributions of nebular scattered radiation prevent direct comparison of measured equivalent widths in the VLT/UVES and HST/STIS spectra. Fortunately, HST/STIS and VLT/UVES have a small overlap in wavelength coverage which allows us to compare and adjust for the difference in scattered radiation entering the instruments' apertures. This paper provides a complete online VLT/UVES spectrum with line identifications and a spectral comparison between HST/STIS and VLT/UVES between 3060 and 3160 Angstroms.

Nielsen, K. E.↗