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Results for “Optical absorption spectroscopy”

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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Optical Absorption Spectroscopy Probes Water Wire and Its Ordering in a Hydrogen-Bond Network

Water wires, quasi-one-dimensional chains composed of hydrogen-bonded (H-bonded) water molecules, play a fundamental role in numerous chemical, physical, and physiological processes. Yet direct experimental detection of water wires has been elusive so far. Based on advanced many-body theory that includes electron-hole interactions, we report that optical absorption spectroscopy can serve as a sensitive probe of water wires and their ordering. In both liquid and solid water, the main peak of the spectrum is discovered to be a charge-transfer exciton. In water, the charge-transfer exciton is strongly coupled to the H-bonding environment where the exciton is excited between H-bonded water molecules with a large spectral intensity. In regular ice, the spectral weight of the charge-transfer exciton is enhanced by a collective excitation occurring on proton-ordered water wires, whose spectral intensity scales with the ordering length of water wire. The spectral intensity and excitonic interaction strength reaches its maximum in ice XI, where the long-range ordering length yields the most pronounced spectral signal. Our findings suggest that water wires, which widely exist in important physiological and biological systems and other phases of ice, can be directly probed by this approach. Published by the American Physical Society 2025

Tang, Fujie (ORCID:0000000197615359)↗
DOE OSTI2021

Direct Observation of Plasma-Stimulated Activation of Surface Species Using Multimodal In Situ/Operando Spectroscopy Combining Polarization-Modulation Infrared Reflection-Absorption Spectroscopy, Optical Emission Spectroscopy, and Mass Spectrometry

Nonthermal plasmas (NTPs) produce reactive chemical environments, including electrons, ions, radicals, and vibrationally excited molecules, that can drive chemistry at temperatures at which such species are thermally inaccessible. There has been growing interest in the integration of conventional catalysis with reactive NTPs to promote novel chemical transformations. Unveiling the full potential of plasma-catalytic processes requires a comprehensive understanding of plasma-catalytic synergies, including characterization of plasma-catalytic surface interactions. In this work, we report on a newly designed multimodal spectroscopic instrument combining polarization-modulation infrared reflection-absorption spectroscopy (PM-IRAS), mass spectrometry, and optical emission spectroscopy (OES) for the investigation of plasma–surface interactions such as those found in plasma catalysis. In particular, this tool has been utilized to correlate plasma-phase chemistry with both surface chemistry and gas-phase products in situ (1) during the deposition of carbonaceous surface species via NTP-promoted nonoxidative coupling of methane and (2) during subsequent activation of surface deposits with an atmospheric pressure and temperature argon plasma jet on both nickel (Ni) and silicon dioxide (SiO 2 ) surfaces. For the first time, the activation of carbonaceous surface species by a NTP on Ni and SiO 2 surfaces to form hydrogen gas and C 2 hydrocarbons was directly observed, where both PM-IRAS and OES measurements suggest that they may form through different pathways. Furthermore, this unique tool for studying plasma–surface interactions could enable more rational design of plasma-stimulated catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1986

OH radical measurements by optical absorption spectroscopy

The long path absorption spectroscopy (LPA) measurement of OH utilizes the strong UV absorption spectrum of the molecule with well resolved rotational lines around 308 nm. The light source consists of an Ar ion laser pumped CW dye laser, the output of which is frequency doubled to emit a spectrally smooth light profile of 0.1 nm FWHM at 308 nm. This is considerably broader than the sharp (0.0018 nm wide) absorption features of OH and also wider than the total spectral region (0.06 nm) scanned around the OH lines. For field measurements a Cassegrain-type telescope expands the small diameter of the original laser beam by a factor of 50 to about a 0.25-m diameter in order to reduce the divergence of the beam as well as its mean photon flux density, thus reducing the maximum self-generated OH concentration to 40,000 cu. cm. The light is passed into the open atmosphere and reflected at about 5 km distance resulting in a 10-km light path length. A telescope focuses the returning light onto the entrance slit of a monochromator the single exit slit of which is replaced by a mechanical scanning device operating at a scan repetition rate of 6.6 KHz. For a typical measurement (1h duration) some 20,000,000 scans are averaged, rendering the contribution of atmospheric turbulence to the spectral noise negligible.

Platt, U.↗
DOE OSTI2021

Early- and late-time dynamics of laser-produced plasmas by combining emission and absorption spectroscopy

Optical emission spectroscopy and laser absorption spectroscopy are two highly complementary techniques for diagnosing plasmas, specifically in the determination of important parameters such as temperature and density. In this work, we characterized a laser-produced plasma by combining emission and tunable absorption spectroscopy. Plasmas are produced by focusing pulses from a frequency quadrupled Nd:YAG laser onto a glass target containing a minor concentration of aluminum in an ambient atmosphere of ~100 Torr N 2 . Here, emission spectroscopy is used to investigate the line behavior of Al and Ca, electron density, and excitation temperature at times = 5 μs, while absorption spectroscopy is used to investigate the line behavior of Al and Ca, species density, and kinetic temperature at times = 5-100 μs. A comparison is made between the excitation temperature measured from emission using the Boltzmann plot method and the kinetic temperature measured from absorption; the implications of this comparison on local thermodynamic equilibrium and line-of-sight averaging are discussed. By combining the two methods of optical emission and laser absorption spectroscopy, a comprehensive characterization of the plasma over the entire lifetime of its evolution is possible, leading to a greater understanding of the plasma behavior including particle condensation.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2022

Tuning the Charge Transport Property and Photocatalytic Activity of Anthracene-Based 1D π–d Conjugated Coordination Polymers by Interlayer Stacking

One-dimensional (1D) π–d-conjugated coordination polymers (CCPs) with charge delocalization have attracted significant attention due to their potential application in energy conversion and storage. However, the fundamental understanding of the correlation of their structural parameters with photophysical and photocatalytic properties remains underexplored. Herein, we report three novel Cu-node anthracene-based 1D π–d CCPs with systematic variation of steric groups (Ph > Me > H) at the 9 and 10 position of anthracene (denoted as An Ph , An Me , and An H ), which is aimed at altering the stacking of the polymer chains and its impact on the inter-chain charge transport property. Here, by using the combination of steady-state X-ray absorption spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and electrochemical impedance spectroscopy, we show that the linear ligands (An Ph , An Me , and An H ) with different degrees of steric groups (Ph > Me > H) introduced at the 9 and 10 position of anthracene can alter the stacking of the polymer chains and thus impact their crystallinity, charge separation, and charge transport property, which in turn impacts their photocatalytic performance for hydrogen evolution reaction.

1-D-polymer↗
DOE OSTI2025

Ultrafast exciton and trion dynamics in highly 𝑛-doped Mo⁢S 2 monolayers: Many-body effects

Understanding many-body interactions of excitons and charge carriers in monolayer semiconductors is crucial for tuning their unique optical properties and optimizing their performance in optoelectronic devices. However, the sensitivity of these atomically thin semiconductors to doping, defects, and strain–arising from synthesis, substrate, and environmental conditions–hinders consistent observation of many-body effects. In this work, we employed linear and ultrafast transient optical absorption spectroscopy to investigate the influence of background doping on exciton many-body interactions in Mo⁢S 2 monolayers. Using reversible molecular physisorption gating, we achieved a high background doping density of 4.9 × 10 13 c⁢m −2 in an argon environment, which is significantly higher than those attainable with conventional electrical gating. Our results reveal a photoinduced 𝐴-exciton resonance redshift, attributed to band-gap renormalization at a low background-doping density of 4.3 × 10 12 c⁢m −2 in an air environment, transitioning to a blueshift at a high background-doping density of 4.9 × 10 13 c⁢m −2 due to dominant Pauli blocking effects and vertical excitation shifts. We further observed transient energy splitting between free-exciton and -trion states up to 57 meV due to exciton-electron interactions. The ultrafast spectroscopy further revealed exciton and trion dynamics, including fast energy splitting of exciton and trion resonances within 1 picosecond (ps) followed by a rapid decay having a lifetime of ∼5.4 ps. Furthermore, our results demonstrate the critical role of background-doping conditions in tuning many-body interactions and quasiparticle dynamics in 2D semiconductors, providing valuable insights for future device design and material engineering.

Doped semiconductors↗
NASA NTRS1994

UV laser long-path absorption spectroscopy

Long path Differential Optical Absorption Spectroscopy (DOAS) using a picosecond UV laser as a light source was developed in our institute. Tropospheric OH radicals are measured by their rotational absorption lines around 308 nm. The spectra are obtained using a high resolution spectrograph. The detection system has been improved over the formerly used optomechanical scanning device by application of a photodiode array which increased the observed spectral range by a factor of 6 and which utilizes the light much more effectively leading to a considerable reduction of the measurement time. This technique provides direct measurements of OH because the signal is given by the product of the absorption coefficient and the OH concentration along the light path according to Lambert-Beers law. No calibration is needed. Since the integrated absorption coefficient is well known the accuracy of the measurement essentially depends on the extent to which the OH absorption pattern can be detected in the spectra. No interference by self generated OH radicals in the detection lightpath has been observed. The large bandwidth (greater than 0.15 nm) and the high spectral resolution (1.5 pm) allows absolute determination of interferences by other trace gas absorptions. The measurement error is directly accessible from the absorption-signal to baseline-noise ratio in the spectra. The applicability of the method strongly depends on visibility. Elevated concentrations of aerosols lead to considerable attenuation of the laser light which reduces the S/N-ratio. In the moderately polluted air of Julich, where we performed a number of OH measurement spectra. In addition absorption features of unidentified species were frequently detected. A quantitative deconvolution even of the known species is not easy to achieve and can leave residual structures in the spectra. Thus interferences usually increase the noise and deteriorate the OH detection sensitivity. Using diode arrays for sensitive absorption measurements some specific problems of those detectors have to be solved experimentally (i.e. fixed pattern noise, dark signal noise, nonuniform efficiency of individual elements, spatial sensitivity variations). In order to improve the low spatial resolution we performed laboratory studies using a multiple reflection cell to convert the long path technique to a real in situ point measurement. Under the conditions of field experiments in Julich residual absorbance signals at present are about 1.5x10(exp -4) corresponding to an OH detection sensitivity of 2x10(exp 6) OH/cm(exp 3) using a light path of 5.8 km. Total integration times for one measurement point vary between a few minutes and an hour.

Dorn, Hans-Peter↗
NASA NTRS1992

Optical remote measurement of toxic gases

Enactment of the Clean Air Act Amendments (CAAA) of 1990 has resulted in increased ambient air monitoring needs for industry, some of which may be met efficiently using open-path optical remote sensing techniques. These techniques include Fourier transform spectroscopy, differential optical absorption spectroscopy, laser long-path absorption, differential absorption lidar, and gas cell correlation spectroscopy. With this regulatory impetus, it is an opportune time to consider applying these technologies to the remote and/or path-averaged measurement and monitoring of toxic gases covered by the CAAA. This article reviews the optical remote sensing technology and literature for that application.

Review↗
NASA NTRS2005

Instrumentation for Sensitive Gas Measurements

An improved instrument for optical absorption spectroscopy utilizes off-axis paths in an optical cavity in order to increase detection sensitivity while suppressing resonance effects. The instrument is well suited for use in either cavity ring-down spectroscopy (CRDS) [in which one pulses an incident light beam and measures the rate of decay of light in the cavity] or integrated cavity output spectroscopy (ICOS) [in which one uses a continuous-wave incident light beam and measures the power of light in the cavity as a function of wavelength]. Typically, in optical absorption spectroscopy, one seeks to measure absorption of a beam of light in a substance (usually a gas or liquid) in a sample cell. In CRDS or ICOS, the sample cell is placed in (or consists of) an optical cavity, so that one can utilize multiple reflections of the beam to increase the effective optical path length through the absorbing substance and thereby increase the sensitivity for measuring absorption. If an absorbing substance is not present in the optical cavity, one can utilize the multiple passes of the light beam to increase the sensitivity for measuring absorption and scattering by components of the optical cavity itself. It is desirable to suppress the effects of resonances in the cavity in order to make the spectral response of the cavity itself as nearly constant as possible over the entire wavelength range of interest. In the present instrument, the desired flattening of the spectral response is accomplished by utilizing an off-axis beam geometry to effectively decrease the frequency interval between longitudinal electromagnetic modes of the cavity, such that the resulting transmission spectrum of the cavity is nearly continuous: in other words, the cavity becomes a broad-band optical device.

OKeefe, Anthony↗
DOE OSTI2021

Excited-State Bond Contraction and Charge Migration in a Platinum Dimer Complex Characterized by X-ray and Optical Transient Absorption Spectroscopy

Interactions between metal centers in dimeric transition metal complexes (TMCs) play important roles in their excited-state energetics and pathways, and, thus, affect their photophysical properties relevant to their applications, e.g., photoluminescent materials and photocatalysis. In this study, we report electronic and nuclear structural dynamics studies of two photoexcited pyrazolate-bridged [Pt(ppy)(µ-R 2 pz)] 2 -type Pt(II) dimers (ppy = 2-phenylpyridine, µ-R 2 pz = 3,5-substituted pyrazolate): [Pt(ppy)(µ-H 2 pz)] 2 (1) and [Pt(NDI-ppy)(µ-Ph 2 pz)] 2 (2, NDI = 1,4,5,8-naphthalenediimide), both of which have distinct ground state Pt-Pt distances. X-ray transient absorption spectroscopy at the Pt L III -edge revealed a new d-orbital vacancy due to the one-electron oxidation of the Pt centers in 1 and 2. However, while a transient Pt-Pt contraction was observed in 2, such an effect was completely absent in 1, demonstrating how the excited states of these complexes are determined by the overlap of the Pt (d z 2 ) orbitals, which is tuned by steric bulk of the pyrazolate R-groups in the 3- and 5-positions. In tandem with analysis of the Pt-Pt distance structural parameter, we observed photoinduced charge separation in 2 featuring a covalently linked NDI acceptor on the ppy ligand. The formation and subsequent decay of the NDI radical anion absorption signals were detected upon photoexcitation using optical transient absorption spectroscopy. The NDI radical anion decayed on the same timescale, hundreds of picoseconds, as that of the d-orbital vacancy signal of the oxidized Pt-Pt core observed in the XTA measurements. The data indicated ultrafast formation of the charge-separated state and subsequent charge recombination to the original Pt(II-II) species.

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

Characterization of an RF-driven argon plasma at atmospheric pressure using broadband absorption and optical emission spectroscopy

Atmospheric pressure plasmas in argon are of particular interest due to the production of highly excited and reactive species enabling numerous plasma-aided applications. In this contribution, we report on absolute optical emission and absorption spectroscopy of a radio frequency (RF) driven capacitively coupled argon glow discharge operated in a parallel-plate configuration. This enabled the study of all key parameters including electron density and temperature, gas temperature, and absolute densities of atoms in highly electronically excited states. The space and time-averaged electron density and temperature were determined from the measurement of the absolute intensity of the electron-atom bremsstrahlung in the visible range. Considering the non-Maxwellian electron energy distribution function, an electron temperature (T e ) of 2.1 eV and an electron density (n e ) of 1.1 × 10 19 m –3 were obtained. The time-averaged and spatially resolved absolute densities of atoms in the metastable (1s 5 and 1s 3 ) and resonant (1s 4 and 1s 2 ) states of argon in pure Ar and Ar/He mixture were obtained by broadband absorption spectroscopy. The 1s 5 metastable atoms had the largest density near the sheath region with a maximum value of 8 × 10 17 m –3 , while all other 1s states had densities of at most 2 × 10 17 m –3 . Here, the dominant production and loss mechanisms of these atoms were discussed, in particular, the role of radiation trapping. We conclude with a comparison of the plasma properties of the argon RF glow discharges with the more common He equivalent and highlight their differences.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2026

Photoelectron Spectroscopic Determination of the Interfacial Energetics of Metal Oxide Protection Layers on p-InP Photocathodes

The interfacial energetics between p-type InP and a series of metal oxides, including TiO 2 , Nb 2 O 5 , Ta 2 O 5 , and HfO 2 , were evaluated using X-ray photoelectron spectroscopy (XPS), ultraviolet photoelectron spectroscopy (UPS), and optical absorption spectroscopy. The energy of the conduction-band minimum ( E cb ) of TiO 2 and Nb 2 O 5 was more negative (i.e., further from the vacuum level) than the conduction-band minimum at the surface of InP ( E cb,s ), whereas E cb for Ta 2 O 5 and HfO 2 was more positive than E cb,s for InP. The data are consistent with the electrochemical behavior of p-InP coated with various metal oxide candidate protection layers, with TiO 2 and Nb 2 O 5 facilitating interfacial transfer of photogenerated minority-carrier electrons in p-InP photocathodes, and Ta 2 O 5 and HfO 2 blocking photogenerated electrons in p-InP from readily transferring across the oxide-coated photocathodes. The energy of the valence-band maximum ( E vb ) for all of the oxides was much more negative than E vb,s for InP, consistent with observations that these protection layers effectively block hole transport and consequently suppress oxidative degradation of the underlying p-InP photocathodes.

63 RADIATION, THERMAL, AND OTHER ENVIRON. POLLUTAN↗
DOE OSTI2025

Plasmonic Ag nanocomposite phosphate glasses produced via γ-ray irradiation as reduction route

This paper reports on the impact of γ-ray irradiation (10, 100 kGy) on melt-quenched Ag + -doped phosphate glass and the effects of subsequent thermal processing leading to the production of plasmonic Ag nanocomposites. The γ-irradiated glasses were characterized alongside the pristine by differential scanning calorimetry (DSC), Raman spectroscopy, electron paramagnetic resonance (EPR) spectroscopy, optical absorption, and photoluminescence (PL) spectroscopy. DSC characterization showed consistent glass transition temperatures (T g ) before and after γ-irradiation whereas the crystallization temperatures tended to decrease with increasing γ-ray dose. However, a lack of alteration of the glass network structure was supported by Raman spectroscopy. Room temperature EPR spectra clearly showed the formation of phosphorus oxygen hole center (POHC) defects in the undoped host, in addition to another doublet likely associated with a P 3 defect. The presence of paramagnetic silver species encompassing Ag 2+ and 107/109 Ag 0 atoms was also indicated in the silver-activated glass together with POHC defects. Optical absorption spectra were also consistent with the presence of various radiation-induced centers. Further analyzing the glass absorption edge via Tauc plots suggested the formation of electron center (EC) defects in γ-irradiated samples wherein the silver-doped glass exhibited decreasing band gap energies with increasing γ-ray dose. The PL characterization showed the silver-related radio-PL effect was induced exhibiting broad band emission with two maxima around 500 and 625 nm stemming from various molecular Ag$^{x+}_{n}$ clusters. Emission decay analyses revealed that the longer wavelength emission exhibited slower decay. The highest radiation dose of 100 kGy however resulted in weaker emission and faster decay kinetics attributed to energy transfer between the luminescent silver species and POHC defects. Finally subjecting the γ-irradiated Ag-doped glasses to heat treatment near the T g at 490 °C led to the development of the surface plasmon resonance of Ag nanoparticles (NPs) and the vanishing of the Ag$^{x+}_{n}$ clusters luminescence. In conclusion, the presence of the matrix-related EC defects was deemed accountable for the thermally induced reduction and consequent precipitation of Ag NPs making the plasmonic glasses attractive for photonic applications such as nonlinear optics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Dynamic computational optical fringe mitigation in tunable laser absorption spectroscopy

In optical spectroscopic systems where unwanted optical scattering cannot be eliminated, Fabry-Pérot etalons cause unpredictable changes in the spectral background. Frequent system calibration is then required to maintain the desired measurement accuracy, which presents a major limitation to the spectrometer. We introduce a computational approach to mitigate the adverse effects of optical fringing without hardware modifications. Motivated by experimental observations of complicated fringe behaviors, we simplify the problem by decomposing the fringe background into component etalons that can be addressed according to their individual characteristics. The effectiveness of the proposed method is demonstrated on a silicon photonic methane sensor, where accurate measurements of methane concentration are obtained from spectral data strongly affected by optical fringes.

Teng, Chu C. (ORCID:0000000152744835)↗
DOE OSTI2020

Tunable Perovskite-Derived Bismuth Halides: Cs 3 Bi 2 (Cl 1– x I x ) 9

Bismuth-based perovskites are of interest as safer alternatives to lead-based optoelectronic materials. Prior studies have reported on the compounds Cs 3 Bi 2 Cl 9 , Cs 3 Bi 2 I 9 , and Cs 3 Bi 2 Cl 3 I 6 . Here we examine a range of compounds of the formula Cs 3 Bi 2 (Cl 1–x I x ) 9 , where x takes values from 0.09 to 0.52. Powder and single-crystal X-ray diffraction were used to determine that all of these compounds adopt the layered vacancy-ordered perovskite structure observed for Cs 3 Bi 2 Cl 3 I 6 , which is also the high-temperature phase of Cs 3 Bi 2 Cl 9 . We find that, even with very small iodine incorporation, the structure is switched to that of Cs 3 Bi 2 Cl 3 I 6 , with I atoms displaying a distinct preference for the capping sites on the BiX 6 octahedra. Optical absorption spectroscopy was employed to study the evolution of optical properties of these materials, and this is complemented by density functional theory electronic structure calculations. Finally, three main absorption features were observed for these compounds, and with increasing x, the lowest-energy features are red-shifted.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗