Search NASA⌕ Search

SEARCH · Search NASA

Results for “split spectrum”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
DOE OSTI2015

Magnetic control of valley pseudospin in monolayer WSe 2

Local energy extrema of the bands in momentum space, or valleys, can endow electrons in solids with pseudo-spin in addition to real spin 1-5 . In transition metal dichalcogenides this valley pseudo-spin, like real spin, is associated with a magnetic moment1,6 which underlies the valley-dependent circular dichroism 6 that allows optical generation of valley polarization 7-9 , intervalley quantum coherence 10 , and the valley Hall effect 11 . However, magnetic manipulation of valley pseudospin via this magnetic moment 12-13 , analogous to what is possible with real spin, has not been shown before. Here we report observation of the valley Zeeman splitting and magnetic tuning of polarization and coherence of the excitonic valley pseudospin, by performing polarization-resolved magneto-photoluminescence on monolayer WSe 2 . Our measurements reveal both the atomic orbital and lattice contributions to the valley orbital magnetic moment; demonstrate the deviation of the band edges in the valleys from an exact massive Dirac fermion model; and reveal a striking difference between the magnetic responses of neutral and charged valley excitons which is explained by renormalization of the excitonic spectrum due to strong exchange interactions.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2018

High resolution magnetic field measurements in hydrogen and helium plasmas using active laser spectroscopy

Passive spectroscopic measurements of Zeeman splitting have been used reliably to measure magnetic fields in plasmas for decades. However, a requirement is that the field magnitude must be sufficiently strong to be resolved over Doppler and instrument broadening (typically >10 000 G). A diagnostic for measuring magnetic fields spectroscopically well below this limit (>20 G) with high sensitivity has been developed at the Oak Ridge National Laboratory. The diagnostic relies on measuring a high resolution spectral profile using Doppler-free saturation spectroscopy (DFSS) and then fitting the spectrum to a quantum mechanical model. DFSS is an active, laser based technique that greatly reduces the influence of Doppler broadening and eliminates instrument broadening. To date, the diagnostic has been successfully employed to measure the magnetic field in magnetized (550-900 G), low-temperature (5-10 eV), low-density (10 10 –10 12 cm –3 ), hydrogen and helium plasmas in the 5-200 mTorr pressure range using a low power (25 mW) diode laser. Implementing an approximate crossover resonance model, the measurements are shown to be accurate within 5 G for helium and 83 G for hydrogen. The accuracy in hydrogen can be improved to 39 G if the crossover resonances are neglected. As a result, a more robust crossover model can decrease this error to <1 G.

47 OTHER INSTRUMENTATION↗
DOE OSTI2018

Spin-orbit coupled systems in the atomic limit: rhenates, osmates, iridates

Motivated by RIXS experiments on a wide range of complex heavy oxides, including rhenates, osmates, and iridates, we discuss the theory of RIXS for site-localized t 2 g orbital systems with strong spin-orbit coupling. For such systems, we present exact diagonalization results for the spectrum at different electron fillings, showing that it accesses “single-particle” and “multiparticle” excitations. This leads to a simple picture for the energies and intensities of the RIXS spectra in Mott insulators such as double perovskites which feature highly localized electrons, and yields estimates of the spin-orbit coupling and Hund's coupling in correlated 5d oxides. We present new higher resolution RIXS data at the Re L 3 edge in Ba 2 YReO 6 which finds a previously unresolved peak splitting, providing further confirmation of our theoretical predictions. Using ab initio electronic structure calculations on Ba 2 MReO 6 (with M=Re, Os, Ir) we show that while the atomic limit yields a reasonable effective Hamiltonian description of the experimental observations, effects such as t 2 g –e g interactions and hybridization with oxygen are important. Our ab initio estimate for the strength of the intersite exchange coupling shows that, compared to the d 3 systems, the exchange is one or two orders of magnitude weaker in the d 2 and d 4 materials, which may partly explain the suppression of long-range magnetic order in the latter compounds. As a way to interpolate between the site-localized picture and our electronic structure band calculations, we discuss the spin-orbital levels of the MO 6 cluster. In conclusion, this suggests a possible role for intracluster excitons in Ba 2 YIrO 6 which may lead to a weak breakdown of the atomic J eff = 0 picture and to small magnetic moments.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS2003

Symmetric Waveguide Orthomode Junctions

Imaging applications at millimeter and submillimeter wavelengths demand precise characterization of the amplitude, spectrum, and polarization of the electromagnetic radiation. The use of a waveguide orthomode transducer (OMT) can help achieve these goals by increasing spectral coverage and sensitivity while reducing exit aperture size, optical spill, instrumental polarization offsets, and lending itself to integration in focal plane arrays. For these reasons, four-fold symmetric OMTs are favored over a traditional quasi-optical wire grid for focal plane imaging arrays from a systems perspective. The design, fabrication, and test of OMTs realized with conventional split-block techniques for millimeter wave-bands are described. The design provides a return loss is -20 dB over a full waveguide band (40% bandwidth), and the cross-polarization and isolation are greater than -40 dB for tolerances readily achievable in practice. Prototype examples realized in WR10.0 and WR3.7 wavebands will be considered in detail.

Wollack, E. J.↗
NASA NTRS2003

Symmetric Waveguide Orthomode Junctions

Imaging applications at millimeter and submillimeter wavelengths demand precise characterization of the amplitude, spectrum, and polarization of the electromagnetic radiation. The use of a waveguide orthomode transducer (OMT) can help achieve these goals by increasing spectral coverage and sensitivity while reducing exit aperture size, optical spill, instrumental polarization offsets, and lending itself to integration in focal plane arrays. For these reasons, four-old symmetric OMTs are favored over a traditional quasi-optical wire grid for focal plane imaging arrays from a systems perspective. The design, fabrication, and test of OMTs realized with conventional split-block techniques for millimeter wave-bands are described. The design provides a return loss is -20 dB over a full waveguide band (40% bandwidth), and the cross-polarization and isolation are greater than -40 dB for tolerances readily achievable in practice. Prototype examples realized in WR10.0 and WR3.7 wavebands will be considered in detail.

Wollack, E. J.↗
DOE OSTI2018

Extracting Chemical Information from XPS Spectra: A Perspective

Important mechanisms that lead to features, often complex, in X-ray photoelectron spectroscopy (XPS) spectra are defined and described. It is shown that there is much information in an XPS spectrum that can be obtained by examining these features rather than examining only the shifts of main peaks between different materials. These mechanisms are presented with a focus on describing the underlying chemical and physical phenomena responsible for features of the XPS and on showing how these XPS features can be related to the properties and electronic structure of the material studied. While it is necessary to consider certain quantum mechanical rules, the mathematical formalism is not discussed. However, a general awareness of multiplet splittings, which are a result of angular momentum coupling combined with ligand field and spin-orbit splittings, and of covalent mixings in the metal-ligand bond of oxides is essential to properly interpret the significance of XPS features. A conceptual framework of shake excitation from bonding to anti-bonding orbitals is introduced to provide an understanding of the significance of XPS satellites. While the coupling of theory and measurement is required to extract quantitative information from XPS, it may be possible to obtain useful qualitative information directly from features of the XPS spectra provided that one takes into account more than only shifts of the XPS binding energies.

Bagus, Paul S.↗
NASA NTRS1990

A comparison of internal energy calculation methods for diatomic molecules

Various methods of calculating the internal energy of diatomic molecules are studied. An accurate and efficient method for computing the eigenvalues of the vibrational Schroedinger equation for an arbitrary potential is developed. The method is based on a finite-element discretization using the cubic Lobatto element. A combination of spectrum slicing and the Laguerre algorithm is used to solve for the eigenvalues. A simple method to compute the quasi-bound states is presented. For N2 molecules, all vibrational-rotational states of eleven available electronic potentials are computed, and summed to obtain the exact internal energy function with temperature. The total computation required 314 seconds of CPU-time on NASA's Cray 2 computer. Various approximate models are discussed and compared with the exact numerical simulation. It is shown that the splitting of the macroscopic internal energy into separate electronic, rotational, and vibrational energies is not justified at high temperatures.

Liu, Yen↗
NASA NTRS2011

Landsat Data Continuity Mission

The Landsat Data Continuity Mission (LDCM) is currently under development and is on schedule to launch the 8th satellite in the Landsat series in December of 2012. LDCM is a joint project between the National Aeronautics and Space Administration (NASA) and the United States Geological Survey (USGS). NASA is responsible for developing and launching the flight hardware and on-orbit commissioning and USGS is responsible for developing the ground system and operating the system onorbit after commissioning. Key components of the flight hardware are the Operational Land Imager (OLI), nearing completion by Ball Aerospace & Technologies Corp in Boulder, CO, the Thermal Infrared Sensor (TIRS), being built by NASA's Goddard Space Flight Center and the spacecraft, undergoing integration at Orbital Sciences Corp in Gilbert, Arizona. The launch vehicle will be an Atlas-5 with launch services provided by NASA's Kennedy Space Center. Key ground systems elements are the Mission Operations Element, being developed by the Hammers Corporation, and the Collection Activity Planning Element, Ground Network Element, and Data Processing and Archive System, being developed internally by the USGS Earth Resources Observations and Science (EROS) Center. The primary measurement goal of LDCM is to continue the global coverage of moderate spatial resolution imagery providing continuity with the existing Landsat record. The science goal for this imagery is to monitor land use and land cover, particularly as it relates to global climate change. Together the OLI and TIRS instruments on LDCM replace the ETM+ instrument on Landsat-7 with significant enhancements. The OLI is a pushbroom design instrument where the scanning mechanism of the ETM+ is effectively replaced by a long line of detectors. The OLI has 9 spectral bands with similar spatial resolution to ETM+: 7 of them similar to the reflective spectral bands on ETM+ and two new bands. The two new bands cover (1) the shorter wavelength blue part of the spectrum to help with coastal studies and aerosol analyses/atmospheric correction and (2) an atmospheric water absorption band, where the Earth surface is generally not visible, but Cirrus clouds are, to aid in cloud detection and screening. The radiometry of OLI benefits from improved SNR, dynamic range and quantization. OLI is undergoing system testing with a delivery scheduled for Spring 2011. The TIRS is also a pushbroom design and used QWIPS detectors that require cooling to 43K using a cryocooler. It.has two spectral bands, effectively splitting the ETM+ band 6 in half, that can be used as a split window to aid in atmospheric correction. It has nominally 100 m spatial resolution as opposed to the 60 m of Landsat-7 ETM+: TIRS has commenced integration and test, with a delivery to the spacecraft vendor scheduled for Winter 2011-2012. The Orbital spacecraft currently being integrated for LDCM will have improved capabilities for pointing over previous missions. These capabilities will allow the OLI and TIRS instruments to point off-nadir the equivalent of one WRS-2 path to increase the chances of coverage for high priority targets, particularly in the event of natural disasters. Also, the pointing capability will allow the calibration of the OLI using the sun (roughly weekly), the moon (monthly), stars (during commissioning) and the Earth (at 90 deg from normal orientation, a.k.a., side slither) quarterly. The solar calibration will be used for OLI absolute and relative calibration, the moon for trending the stability of the OLI response, the stars will be used for Line of Sight determination and the side slither will be an alternate OLI and relative gain determination methodology. The spacecraft is scheduled to begin integration with the OLI instrument in Summer 2011. The LDCM data processing and archive system (DPAS), located at USGS EROS, generates the products for distribution to users. Like Landsat-7 this includes an image assessment system for characrizing instrument performance and updating calibration parameters. Products will be generated that include the spectral bands from both instruments, terrain corrected and registered to the geoid. Also, like Landsat-7, data products will be distributed at no charge to the user. The current status and plans of the space and ground segments of the LDCM project will be presented along with performance predictions as available. More detailed information on the two instruments is intended to be presented in separate papers.

Markham, Brian↗
DOE OSTI2015

Three-dimensional spectrum mapping of bright emission centers: Investigating the brightness-limiting process in Eu-doped GaN red light emitting diodes

A pulse-driven emission-spectroscopy mapping technique is used to investigate the bright emission centers in Eu-doped GaN (GaN:Eu) red light emitting diodes (LED). The LEDs are operated in pulse-driven mode, and the emission spectra are acquired for a range of pulse frequencies. This ensemble of emission spectral data yields a three-dimensional mapping that allows the origin of emission lines to be identified by visual inspection. The identification was achieved even for a weak {sup 5}D{sub 0} → {sup 7}F{sub 3} transition in conventional photoluminescence measurements. A peculiar split is observed in the {sup 5}D{sub 0} → {sup 7}F{sub 3} transition for the bright emission center referred to as OMVPE 8. Despite the unique transition at this emission center, the emission efficiencies for the {sup 5}D{sub 0} → {sup 7}F{sub 3} and {sup 5}D{sub 0} → {sup 7}F{sub 2} transitions were identical. This finding indicates that the excitation of the emission centers, rather than the radiative transitions, is the limiting process that determines the GaN:Eu red LED brightness.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2023

Modular chip-integrated photonic control of artificial atoms in diamond waveguides

A central goal in creating long-distance quantum networks and distributed quantum computing is the development of interconnected and individually controlled qubit nodes. Atom-like emitters in diamond have emerged as a leading system for optically networked quantum memories, motivating the development of visible-spectrum, multi-channel photonic integrated circuit (PIC) systems for scalable atom control. However, it has remained an open challenge to realize optical programmability with a qubit layer that can achieve high optical detection probability over many optical channels. Here, we address this problem by introducing a modular architecture of piezoelectrically actuated atom-control PICs (APICs) and artificial atoms embedded in diamond nanostructures designed for high-efficiency free-space collection. The high-speed four-channel APIC is based on a splitting tree mesh with triple-phase shifter Mach–Zehnder interferometers. This design simultaneously achieves optically broadband operation at visible wavelengths, high-fidelity switching (>40dB) at low voltages, submicrosecond modulation timescales (>30MHz), and minimal channel-to-channel crosstalk for repeatable optical pulse carving. Via a reconfigurable free-space interconnect, we use the APIC to address single silicon vacancy color centers in individual diamond waveguides with inverse tapered couplers, achieving efficient single photon detection probabilities (∼15%) and second-order autocorrelation measurements g (2) (0)<0.14 for all channels. The modularity of this distributed APIC–quantum memory system simplifies the quantum control problem, potentially enabling further scaling to thousands of channels.

47 OTHER INSTRUMENTATION↗
DOE OSTI2014

The interaction of organic adsorbate vibrations with substrate lattice waves in methyl-Si(111)-(1 × 1)

A combined helium atom scattering and density functional perturbation theory study has been performed to elucidate the surface phonon dispersion relations for both the CH{sub 3}-Si(111)-(1 × 1) and CD{sub 3}-Si(111)-(1 × 1) surfaces. The combination of experimental and theoretical methods has allowed characterization of the interactions between the low energy vibrations of the adsorbate and the lattice waves of the underlying substrate, as well as characterization of the interactions between neighboring methyl groups, across the entire wavevector resolved vibrational energy spectrum of each system. The Rayleigh wave was found to hybridize with the surface rocking libration near the surface Brillouin zone edge at both the M{sup ¯}-point and K{sup ¯}-point. The calculations indicated that the range of possible energies for the potential barrier to the methyl rotation about the Si-C axis is sufficient to prevent the free rotation of the methyl groups at a room temperature interface. The density functional perturbation theory calculations revealed several other surface phonons that experienced mode-splitting arising from the mutual interaction of adjacent methyl groups. The theory identified a Lucas pair that exists just below the silicon optical bands. For both the CH{sub 3}- and CD{sub 3}-terminated Si(111) surfaces, the deformations of the methyl groups were examined and compared to previous experimental and theoretical work on the nature of the surface vibrations. The calculations indicated a splitting of the asymmetric deformation of the methyl group near the zone edges due to steric interactions of adjacent methyl groups. The observed shifts in vibrational energies of the -CD{sub 3} groups were consistent with the expected effect of isotopic substitution in this system.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

MEASUREMENTS OF STELLAR MAGNETIC FIELDS USING AUTOCORRELATION OF SPECTRA

We present a novel technique that uses the autocorrelation of the spectrum of a star to measure the line broadening caused by the modulus of its average surface magnetic field. The advantage of the autocorrelation comes from the fact that it can detect very small spectral line broadening effects because it averages over many spectral lines and therefore gives an average with a very high signal-to-noise ratio. We validate the technique with the spectra of known magnetic stars and obtain autocorrelation curves that are in full agreement with published magnetic curves obtained with Zeeman splitting. The autocorrelation also gives less noisy curves so that it can be used to obtain very accurate curves. We degrade the resolution of the spectra of these magnetic stars to lower spectral resolutions where the Zeeman splitting is undetectable. At these resolutions, the autocorrelation still gives good quality curves, thereby showing that it can be used to measure magnetic fields in spectra where the Zeeman splitting is significantly smaller than the width of the spectral line. This would therefore allow observing magnetic fields in very faint Ap stars with low-resolution spectrographs, thereby greatly increasing the number of known magnetic stars. It also demonstrates that the autocorrelation can measure magnetic fields in rapidly rotating stars as well as weak magnetic fields that give a Zeeman splitting smaller than the intrinsic width of the spectral lines. Finally, it shows that the autocorrelation can be used to find unknown magnetic stars in low-resolution spectroscopic surveys.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRSDate not supplied

Classifying Agnostic Biosignatures using Raman, VNIR, and Elemental Data

How can we use our current wealth of terrestrial data, encompassing biogenic and abiogenic systems, to determine the distinguishing properties of life? SCOBI (Statistical Classification of Biosignature Information) uses machine learning techniques to algorithmically identify combinations of measurements that are “indicative of life”. A set of ~1000 observations, comprising elemental abundance, isotopic fractionation, VNIR reflectance, and (in progress) Raman spectra, have been assembled from existing literature and databases. The observations cover systems classified as “indicative alive” (e.g., cells, vegetation), “indicative non-alive” (e.g., fossils, teeth), “mixed indicative” (e.g., soil, pond water), or “non-indicative” (e.g., rocks, meteorites). VNIR data was preprocessed by linear interpolation from 400-2100 nm and smoothed with a Savitzky-Golay filter. To limit the amount of Earth-biochemistry-specific (non-agnostic) information included, the first five spectral features extracted were number of peaks, number of troughs, mean reflectance, mean peak width, and broadest peak width. To help further emphasize agnostic biosignatures, Earth-specific features such as chlorophylls have been manually flagged so that feature importance with and without them can be compared. Classifiers including k-nearest neighbors (KNN), Gaussian Naïve Bayes (GNB), logistic regression (LR), random forest (RF), and support vector machine (SVM) were implemented, as was a combination voting classifier. Performance metrics included false positive rates, false negative rates, and AUC with 50-50 test/train splits (Monte Carlo simulations). Key takeaways from this stage, prior to the inclusion of Raman spectra, are (1) the overall success rate of 0.933 AUC was most heavily influenced by the elemental abundance data; and (2) VNIR reflectance had the lowest classification performance with 0.52 AUC (58% of objects correctly classified). The next steps are to complete integration of Raman spectral data and to improve the approach to pre-processing and feature extraction for both types of spectral data, such as automated baseline removal, whole spectrum matching, and dimensionality reduction.

Biosignatures↗
DOE OSTI2023

Weak-coupling theory of neutron scattering as a probe of altermagnetism

Inelastic neutron scattering provides a powerful probe of the magnetic excitations of quantum magnets. Altermagnets have recently emerged as a new class of magnets with vanishing net magnetization characteristic of antiferromagnets and with a spin-split electronic structure typical of ferromagnets. Here we introduce a minimal Hubbard model with two-sublattice orthorhombic anisotropy as a framework to study altermagnetism. Using unrestricted Hartree-Fock calculations, we find an altermagnetic state for this model that evolves from a metallic state to an insulating state with increasing Hubbard-U Coulomb repulsion. We then examine the inelastic neutron scattering response in these states using random-phase approximation calculations of the dynamic spin susceptibility χ"(q,ω). We find that the magnetic excitation spectrum depends on its chirality for q along certain directions in reciprocal space, an observation that may be used in inelastic neutron scattering experiments as a probe of altermagnetism.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2025

Open Specy 1.0: Automated (Hyper)spectroscopy for Microplastics

Microplastic spectral analysis is one of the most time-consuming processes in studying microplastic pollution, often requiring days per sample. Researchers are transitioning to automated batch and hyperspectral image analysis techniques to enhance efficiency. Open Specy, initially aimed at manual single-spectrum analysis, has now integrated automated methods. This updated version, Open Specy 1.0, introduces several new features, including two algorithms for automated processing (smoothing and particle compression), an extensive library containing over 40,000 open-source Raman and FTIR spectra, and two machine learning classifiers (logistic regression and k medoids) developed from this library. Furthermore, it includes a revamped user interface, an R package, and a benchmark data set for testing future advancements in automated techniques. Researchers evaluated various configurations for hyperspectral smoothing, particle identification, compression, and splitting, to achieve combined recovery rates between 50 and 150% particle counts, identities, and sizes with a coefficient of variation (CV) of less than 40% (the accredited standard). Mean absorbance times the standard deviation provided a consistent particle identification. Hyperspectral smoothing led to a 96% combined recovery rate and reduced variability (CV = 38%) compared to the 86% recovery (CV = 83%) of nonsmoothed controls. Additionally, compressing spectra for particles was significantly faster (>3x) and showed similar accuracy but with reduced variability than processing each pixel individually. Key challenges persist in automating spectral analysis, particularly in refining particle splitting algorithms, and improving identification routines to minimize false positives and negatives. In conclusion, new methods in sample preparation for better stabilization and dispersion of particles could overcome some of these issues.

13 HYDRO ENERGY↗
DOE OSTI2018

Spatial heterodyne spectroscopy for high speed measurements of Stark split neutral beam emission in a high temperature plasma

Measurement of electrostatic potential, or local electric field, turbulence is a critical missing component in validating nonlinear turbulence and transport simulations of fusion plasmas. A novel diagnostic is being developed for measuring local electric field fluctuations, $\sim\atop{E}$(r,t), via high-speed measurements of the light emitted from a hydrogenic neutral beam. It exploits the proportionality of the spectral line splitting from the Motional Stark Effect to the total electric field experienced by the neutral atom at the excitation site. The measurement is localized by the usual cross-beam geometry of beam-spectroscopy measurements. The corner stone of the diagnostic is a high spectral resolution, high etendue spatial heterodyne spectrometer (SHS). A SHS design with high etendue (~5 mm 2 sr) and resolution (~0.14 nm) meets the formidable spectrometer requirements. Field tests of the spectrometer at the DIII-D tokamak demonstrate that the beam emission spectrum produced by the SHS agrees with that of a traditional spectrometer and that the measured flux is adequate for turbulence studies.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2017

Heavy-quark meson spectrum tests of the Oktay–Kronfeld action

The Oktay-Kronfeld (OK) action extends the Fermilab improvement program for massive Wilson fermions to higher order in suitable power-counting schemes. It includes dimension-six and -seven operators necessary for matching to QCD through order ${\mathrm{O}}(\Lambda^3/m_Q^3)$ in HQET power counting, for applications to heavy-light systems, and ${\mathrm{O}}(v^6)$ in NRQCD power counting, for applications to quarkonia. In the Symanzik power counting of lattice gauge theory near the continuum limit, the OK action includes all ${\mathrm{O}}(a^2)$ and some ${\mathrm{O}}(a^3)$ terms. To assess whether the theoretical improvement is realized in practice, we study combinations of heavy-strange and quarkonia masses and mass splittings, designed to isolate heavy-quark discretization effects. We find that, with one exception, the results obtained with the tree-level-matched OK action are significantly closer to the continuum limit than the results obtained with the Fermilab action. The exception is the hyperfine splitting of the bottom-strange system, for which our statistical errors are too large to draw a firm conclusion. Lastly, these studies are carried out with data generated with the tadpole-improved Fermilab and OK actions on 500 gauge configurations from one of MILC's $a\approx0.12$~fm, $N_f=2+1$-flavor, asqtad-staggered ensembles.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2014

Probing the electronic structure and Au–C chemical bonding in AuC{sub 2}{sup −} and AuC{sub 2} using high-resolution photoelectron spectroscopy

We report photoelectron spectroscopy (PES) and high-resolution PE imaging of AuC{sub 2}{sup −} at a wide range of photon energies. The ground state of AuC{sub 2}{sup −} is found to be linear (C{sub ∞v}, {sup 1}Σ{sup +}) with a …8π{sup 4}4δ{sup 4}17σ{sup 2}9π{sup 4}18σ{sup 2} valence configuration. Detachments from all the five valence orbitals of the ground state of AuC{sub 2}{sup −} are observed at 193 nm. High-resolution PE images are obtained in the energy range from 830 to 330 nm, revealing complicated vibronic structures from electron detachment of the 18σ, 9π, and 17σ orbitals. Detachment from the 18σ orbital results in the {sup 2}Σ{sup +} ground state of neutral AuC{sub 2}, which, however, is bent due to strong vibronic coupling with the nearby {sup 2}Π state from detachment of a 9π electron. The {sup 2}Σ{sup +}–{sup 2}Π vibronic and spin-orbit coupling results in complicated vibronic structures for the {sup 2}Σ{sup +} and {sup 2}Π{sub 3/2} states with extensive bending excitations. The electron affinity of AuC{sub 2} is measured accurately to be 3.2192(7) eV with a ground state bending frequency of 195(6) cm{sup −1}. The first excited state ({sup 2}A′) of AuC{sub 2}, corresponding to the {sup 2}Π{sub 3/2} state at the linear geometry, is only 0.0021 eV above the ground state ({sup 2}A′) and has a bending frequency of 207(6) cm{sup −1}. The {sup 2}Π{sub 1/2} state, 0.2291 eV above the ground state, is linear with little geometry change relative to the anion ground state. The detachment of the 17σ orbital also results in complicated vibronic structures, suggesting again a bent state due to possible vibronic coupling with the lower {sup 2}Π state. The spectrum at 193 nm shows the presence of a minor species with less than 2% intensity relative to the ground state of AuC{sub 2}{sup −}. High-resolution data of the minor species reveal several vibrational progressions in the Au–C stretching mode, which are assigned to be from the metastable {sup 3}Π{sub 2,1,0} spin-orbit excited states of AuC{sub 2}{sup −} to the {sup 2}Π{sub 3/2,1/2} spin-orbit states of neutral AuC{sub 2}. The spin-orbit splittings of the {sup 3}Π and {sup 2}Π states are accurately measured at the linear geometry. The current study provides a wealth of electronic structure information about AuC{sub 2}{sup −} and AuC{sub 2}, which are ideal systems to investigate the strong Σ–Π and spin-orbit vibronic couplings.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗