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High-resolution broadband spectroscopy using externally dispersed interferometry at the Hale telescope: Part 2, photon noise theory

High-resolution broadband spectroscopy at near-infrared (NIR) wavelengths (950 to 2450 nm) has been performed using externally dispersed interferometry (EDI) at the Hale telescope at Mt. Palomar, with the TEDI interferometer mounted within the central hole of the 200-in. primary mirror in series with the comounted TripleSpec NIR echelle spectrograph. These are the first multidelay EDI demonstrations on starlight. We demonstrated very high (10×) resolution boost and dramatic (20× or more) robustness to point spread function wavelength drifts in the native spectrograph. Data analysis, results, and instrument noise are described in a companion paper (part 1). This part 2 describes theoretical photon limited and readout noise limited behaviors, using simulated spectra and instrument model with noise added at the detector. We show that a single interferometer delay can be used to reduce the high frequency noise at the original resolution (1× boost case), and that except for delays much smaller than the native response peak half width, the fringing and nonfringing noises act uncorrelated and add in quadrature. This is due to the frequency shifting of the noise due to the heterodyning effect. We find a sum rule for the noise variance for multiple delays. The multiple delay EDI using a Gaussian distribution of exposure times has noise-to-signal ratio for photon-limited noise similar to a classical spectrograph with reduced slitwidth and reduced flux, proportional to the square root of resolution boost achieved, but without the focal spot limitation and pixel spacing Nyquist limitations. At low boost (~1×) EDI has ~1.4× smaller noise than conventional, and at >10× boost, EDI has ~1.4× larger noise than conventional. Readout noise is minimized by the use of three or four steps instead of 10 of TEDI. Net noise grows as step phases change from symmetrical arrangement with wavenumber across the band. As a result, for three (or four) steps, we calculate a multiplicative bandwidth of 1.8:1 (2.3:1), sufficient to handle the visible band (400 to 700 nm, 1.8:1) and most of TripleSpec (2.6:1).

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Special Section Guest Editorial: Active Spectroscopy

A special edition of the journal Optical Engineering invited several scientists to participate in the editorial board of this special issue. The eleven papers in this special section cover recent developments in active spectroscopy, including new phenomenology and applications, advances in systems and components, and new methods for data processing and exploitation.

42 ENGINEERING↗

Evolution of anatase surface active sites probed by in situ sum-frequency phonon spectroscopy

Surface active sites of crystals often govern their relevant surface chemistry, yet to monitor them in situ in real atmosphere remains a challenge. Using surface-specific sum-frequency spectroscopy, we identified the surface phonon mode associated with the active sites of undercoordinated titanium ions and conjoint oxygen vacancies, and used it to monitor them on anatase (TiO 2 ) (101) under ambient conditions. In conjunction with theory, we determined related surface structure around the active sites and tracked the evolution of oxygen vacancies under ultraviolet irradiation. We further found that unlike in vacuum, the surface oxygen vacancies, which dominate the surface reactivity, are strongly regulated by ambient gas molecules, including methanol and water, as well as weakly associated species, such as nitrogen and hydrogen. The result revealed a rich interplay between prevailing ambient species and surface reactivity, which can be omnipresent in environmental and catalytic applications of titanium dioxides.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Determination of the Mode of Occurrence of V, Fe, and Mn in Slags and Charge of Vanadium Production by X-Ray Spectroscopy

Samples of technogenic raw materials are studied by spectroscopic methods. The chemical composition of a roast slag and a charge of vanadium production is analyzed by the X-ray fluorescence method (XRF). The possibilities of X-ray photoelectron spectroscopy are studied for determination of the oxidation state of elements in technogenic raw materials. It is found that ~30% of V occurs in the slag as V(III), whereas, in the charge, the content of V(V) and V(IV) is ~80 and 20%, respectively; no V compounds with the lowest oxidation states are found. Iron in the slag and charge samples is present as Fe{sub 3}O{sub 4}, and Mn mostly occurs as Mn(III). The oxidation state of V in the slag and charge can be determined by the intensity ratio of the K and L lines of the XRF spectra; however, this method is not recommended because of its low accuracy.

36 MATERIALS SCIENCE↗

Soft X-ray absorption spectroscopy of titanium dioxide nanopowders with cobalt impurities

The charge states of the cobalt ions in TiO{sub 2} nanopowders with the anatase lattice are studied by soft X-ray absorption spectroscopy. It is found that, at a low cobalt impurity concentration (1.8 at %), the cobalt ions with an oxidation state 2+ are mainly located in the tetrahedral (T{sub d}) environment of oxygen ions. Amorphous titanium dioxide exists on the sample surface before heat treatment. Annealing in vacuum or hydrogen leads to the enrichment of the nanoparticle surfaces with Co{sup 2+} ions, a change in the coordination of the remaining part of cobalt ions from octahedral to tetrahedral, stabilization of the anatase structure, and the disappearance of the amorphous phase. The crystal lattice of the samples with a relatively high cobalt concentration (12 at %) is distorted, and annealing does not cause the disappearance of the amorphous phase of TiO{sub 2}. Cobalt is reduced to its metallic state upon hydrogen annealing of the samples with a high cobalt concentration.

36 MATERIALS SCIENCE↗

Electronic and Magnetic States of Pr and Mn in the Pr{sub 1–x}Sr{sub x}MnO{sub 3} Films Studied by XANES and XMCD Spectroscopy

The spectral dependences of X-ray absorption near-edge spectroscopy (XANES) and X-ray magnetic circular dichroism (XMCD) and the field dependences of XMCD near the K edge of Mn and the L{sub 2,3} edges of Pr in the Pr{sub 0.8}Sr{sub 0.2}MnO{sub 3} and Pr{sub 0.6}Sr{sub 0.4}MnO{sub 3} films at T = 90 K are studied. The spectral dependences point to a mixed valence state of Mn and Pr in the films. It is found that, as compared to XANES, XMCD is more sensitive to the valence state of Pr{sup 4+}. The field dependences of XMCD point to ferromagnetic behavior of Mn ions and the Van Vleck paramagnetism of Pr ions, which makes a significant contribution to the total magnetization of the films. It is shown that as the Sr concentration increases, the XMCD intensity at the K edge of Mn increases, which indicates a growth of the total magnetic moment of the film due to an increase in the 4p–3d hybridization.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Multiplexing of frequency-modulation spectroscopy by spread-spectrum codes, demonstrated in continuous-wave LIDAR

Frequency-modulation spectroscopy (FMS) is generally suited to code-division multiplexing, and we demonstrate that capacity in a form of continuous-wave LIDAR, utilizing a sharp CO 2 absorption transition at 1.6 µm in simple ranging setups. The approach retains the advantages of FMS, including coherent detection and good rejection of broad absorption backgrounds. Extensions of this multiplexed approach to the continuous, simultaneous detection of several transitions would come by transmitting an encoded combination of frequency-modulated carriers, each tuned to detect a unique absorption transition. Signal analysis at the receiver involves a simple process of de-multiplexing that, in a general application, reveals targets at various distances and the absorption-related FMS signals in between.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Chirped laser dispersion spectroscopy for spectroscopic chemical sensing with simultaneous range detection

Spectroscopic chemical detection requires knowledge or determination of an optical path for accurate quantification of path-integrated concentration of species. Continuous- wave-laser-based spectroscopic systems operating in an open integrated-path remote sensing configuration are usually not equipped for optical path determination. Here we demonstrate a measurement technique capable of simultaneous spectroscopic chemical quantification and range finding. Here, the range-finding functionality is implemented with chirped laser dispersion spectroscopy. The methodology is potentially useful for remote chemical sensing in a hard-target LIDAR configuration and for automatic calibration of gas cells with unknown or varying lengths.

03 NATURAL GAS↗

Comparison of excitation and kinetic temperatures in a laser-produced plasma using absorption spectroscopy

High-resolution tunable laser absorption spectroscopy is used to measure time-resolved absorption spectra for six neutral uranium transitions in a laser-produced plasma. Here analysis of the spectra shows that kinetic temperatures are similar for all six transitions, but excitation temperatures are higher than kinetic temperatures from 10–100 μs, indicating departures from local thermodynamic equilibrium.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Application of visible and near-infrared spectroscopy to classification of Miscanthus species

Here, the feasibility of visible and near infrared (NIR) spectroscopy as tool to classify Miscanthus samples was explored in this study. Three types of Miscanthus plants, namely, M. sinensis , M. sacchariflorus and M. fIoridulus , were analyzed using a NIR spectrophotometer. Several classification models based on the NIR spectra data were developed using line discriminated analysis (LDA), partial least squares (PLS), least squares support vector machine regression (LSSVR), radial basis function (RBF) and neural network (NN). The principal component analysis (PCA) presented rough classification with overlapping samples, while the models of Line_LSSVR, RBF_LSSVR and RBF_NN presented almost same calibration and validation results. Due to the higher speed of Line_LSSVR than RBF_LSSVR and RBF_NN, we selected the line_LSSVR model as a representative. In our study, the model based on line_LSSVR showed higher accuracy than LDA and PLS models. The total correct classification rates of 87.79 and 96.51% were observed based on LDA and PLS model in the testing set, respectively, while the line_LSSVR showed 99.42% of total correct classification rate. Meanwhile, the lin_LSSVR model in the testing set showed correct classification rate of 100, 100 and 96.77% for M. sinensis , M. sacchariflorus and M. fIoridulus , respectively. The lin_LSSVR model assigned 99.42% of samples to the right groups, except one M. fIoridulus sample. The results demonstrated that NIR spectra combined with a preliminary morphological classification could be an effective and reliable procedure for the classification of Miscanthus species.

59 BASIC BIOLOGICAL SCIENCES↗

NEON AOP Imaging Spectroscopy Survey of Upper East River Colorado Watersheds: Raw-Space Radiance and Observational Variable Dataset

Lawrence Berkeley National Laboratory (LBNL) contracted the National Ecological Observatory Network Airborne Observation Platform (NEON AOP) to observe watersheds of interest near Crested Butte, CO with remotely sensed data including imaging spectroscopy. The flight box design encompassed the watersheds, and flight design targeted a minimum of 30% overlap between adjacent flight lines. The total area surveyed was 334 km2 across 72 lines. Flight lines were oriented north-south for consistency in solar illumination geometry. Seven days were required to cover the flight area. Some areas were flown additional times to improve data quality or temporal coincidence between airborne acquisitions and field sampling. In total, 102 lines were collected and can be downloaded here: https://portal.nersc.gov/wfsfa/doi-10-15485-1617204/. The instrument used for the acquisition was an Airborne Visible-Infrared Imaging Spectrometer - Next Generation (AVIRIS-NG), which records radiance within 426 contiguous spectral bands in the wavelength range from 380 to 2510 nm. The instrument was flown at a target aboveground altitude of 1000 m for a processed data spatial resolution of 1 m. These data are non-orthorectified, radiance data that require further processing prior to use as a surface reflectance data set.

2018 NEON and 2025 CHESS Campaigns↗

Ultrafast Absorption Spectroscopy of Aluminum Plasmas Created by LCLS using Betatron X-Ray Radiation

This document summarizes the goals and accomplishments of a six month-long LDRD project, awarded through the LLNL director Early and Mid Career Recognition (EMCR) program. This project allowed us to support beamtime awarded at the Matter under Extreme Conditions (MEC) end station of the Linac Coherent Light Source (LCLS). The goal of the experiment was to heat metallic samples with the bright x-rays from the LCLS free electron laser. Then, we studied how they relaxed back to equilibrium by probing them with ultrafast x-ray absorption spectroscopy using laser-based betatron radiation. Our work enabled large collaborations between LLNL, SLAC, LBNL, and institutions in France and in the UK, while providing training to undergraduate and graduate students during the experiment. Following this LDRD project, the PI was awarded a 5-year DOE early career research grant to further develop applications of laser-driven x-ray sources for high energy density science experiments and warm dense matter states.

36 MATERIALS SCIENCE↗

Remote methane sensor for emissions from pipelines and compressor stations using chirped-laser dispersion spectroscopy

Leak rates of methane (CH 4 ) from the natural gas supply chain result in lost profit from unsold product, public safety and property concerns due to potential explosion hazards, and a potentially large source of economic damages from legal liabilities. Yet large measurement challenges exist in identifying and quantifying CH 4 leak rates along the vast number and type of components in the natural gas supply chain. This is particularly true of the “midstream” components involved in the gathering, processing, compression, transmission, and storage of natural gas. This project developed and deployed new advances in chirped laser dispersion spectroscopy (CLaDS) to detect methane leaks from pipelines, compressor stations, and other midstream infrastructure from a remote position (standoff detection). The system was deployed from a van to measure fugitive methane leaks from a local compressor station as a proof-of-concept. The technique was validated through mobile laboratory measurements with in-situ sensors as well as controlled releases of methane. The system also mapped a plume from a controlled release of methane by tracking a small unmanned aerial system (sUAS) that carried a corner cube retroreflector which reflected the beam back to the instrument. The drone-based system quantified a leak rate to within 30% of the actual rate and localized the emission location within 5 m of the actual release location at standoff distances of 25-45 m. This sUAS-reflector tracking approach has benefits for mapping leak locations remotely using small drones flying around a facility. Benefits of a commercial sensor with these capabilities include reductions of leaks for pipeline operators (more profit), earlier detection of leaks to avoid catastrophic explosion hazards for public health and to mitigate property damage, and reduced methane emissions to the atmosphere (improving air quality).

03 NATURAL GAS↗

Low Temperature Microcalorimeters for Decay Energy Spectroscopy

Low Temperature Detectors have been used to measure embedded radioisotopes in a measurement mode known as Decay Energy Spectroscopy (DES) since 1992. DES microcalorimeter measurements have been used for applications ranging from neutrino mass measurements to metrology to measurements for safeguards and medical nuclides. While the low temperature detectors have extremely high intrinsic energy resolution (several times better than semiconductor detectors), the energy resolution achieved in practice is strongly dependent on factors such as sample preparation method. This review seeks to present the literature consensus on what has been learned by looking at the energy resolution as a function of various choices of detector, absorber, and sample preparation methods.

47 OTHER INSTRUMENTATION↗

Study on the High-Pressure Behavior of Goethite up to 32 GPa Using X-Ray Diffraction, Raman, and Electrical Impedance Spectroscopy

Goethite is a major iron-bearing sedimentary mineral on Earth. In this study, we conducted in situ high-pressure x-ray diffraction, Raman, and electrical impedance spectroscopy measurements of goethite using a diamond anvil cell (DAC) at room temperature and high pressures up to 32 GPa. We observed feature changes in both the Raman spectra and electrical resistance at about 5 and 11 GPa. However, the x-ray diffraction patterns show no structural phase transition in the entire pressure range of the study. The derived pressure-volume (P-V) data show a smooth compression curve with no clear evidence of any second-order phase transition. Fitting the volumetric data to the second-order Birch–Murnaghan equation of state yields V 0 = 138.9 ± 0.5 Å 3 and K 0 = 126 ± 5 GPa.

58 GEOSCIENCES↗

A 5 × 10{sup 9}M{sub ⊙} BLACK HOLE IN NGC 1277 FROM ADAPTIVE OPTICS SPECTROSCOPY

The nearby lenticular galaxy NGC 1277 is thought to host one of the largest black holes known, however the black hole mass measurement is based on low spatial resolution spectroscopy. In this paper, we present Gemini Near-infrared Integral Field Spectrometer observations assisted by adaptive optics. We map out the galaxy's stellar kinematics within ∼440 pc of the nucleus with an angular resolution that allows us to probe well within the region where the potential from the black hole dominates. We find that the stellar velocity dispersion rises dramatically, reaching ∼550 km s{sup −1} at the center. Through orbit-based, stellar-dynamical models we obtain a black hole mass of (4.9 ± 1.6) × 10{sup 9} M{sub ⊙} (1σ uncertainties). Although the black hole mass measurement is smaller by a factor of ∼3 compared to previous claims based on large-scale kinematics, NGC 1277 does indeed contain one of the most massive black holes detected to date, and the black hole mass is an order of magnitude larger than expectations from the empirical relation between black hole mass and galaxy luminosity. Given the galaxy's similarities to the higher redshift (z ∼ 2) massive quiescent galaxies, NGC 1277 could be a relic, passively evolving since that period. A population of local analogs to the higher redshift quiescent galaxies that also contain over-massive black holes may suggest that black hole growth precedes that of the host galaxy.

79 ASTRONOMY AND ASTROPHYSICS↗