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IR and UV absorption spectra of free radical NCN observed following photolysis of matrix isolated cyanogen nitride
Optical properties, fluorescence, and absorption spectra of reduced nicotinamide adenine dinucleotide
X-ray absorption spectroscopy (XAS) is a commonly employed technique for characterizing functional materials. In particular, X-ray absorption near edge spectra (XANES) encode local coordination and electronic information, and machine learning approaches to extract this information are of significant interest. To date, most ML approaches for XANES have primarily focused on using the raw spectral intensities as input, overlooking the potential benefits of incorporating spectral transformations and dimensionality reduction techniques into ML predictions. Here, in this work, we focused on systematically comparing the impact of different featurization methods on the performance of ML models for XAS analysis. We evaluated the classification and regression capabilities of these models on computed data sets and validated their performance on previously unseen experimental data sets. Our analysis revealed an intriguing discovery: the cumulative distribution function feature achieves both high prediction accuracy and exceptional transferability. This remarkably robust performance can be attributed to its tolerance to horizontal shifts in the spectra, which is crucial when validating models using experimental data. While this work exclusively focuses on XANES analysis, we anticipate that the methodology presented here will hold promise as a versatile asset to the broader spectroscopy community.
The glasses of the composition [xCoO–(29.5 − x)Na{sub 2}O–55B{sub 2}O{sub 3}–15ZnO–0.5Er{sub 2}O{sub 3}] (where x = 0, 0.3, 0.5, 1 and 3 mol%) have been prepared using melt quenching technique. The recorded UV/VIS/NIR absorption spectra have been studied and the resulting data was used for the ligand field theory analysis, from which the crystal field energy (10Dq), Racah parameters (B, C) and nephelauxetic ratio (β) were evaluated. The observed variations in the band gap and Urbach energy with CoO content have been discussed in relation with the glass structure. FT-IR spectra of the samples exhibit modes of vibration corresponding to the stretching of BO{sub 3} and BO{sub 4} unit. From IR studies, the number of non-bridging oxygens was increased, leading to loosen structure at higher CoO concentrations. The ESR spectra revealed that Co{sup 2+} ions are located both in distorted tetrahedral and octahedral sites.
We report the making of a double-beam laser spectrometer to measure absorption spectra in the ν{sub 5} + ν{sub 9} combination vibrational band of ethylene in the region of λ = 1.6 μm. The spectrometer is used to find a portion of the spectrum that has well-resolved absorption lines of all four nuclear spin isomers of ethylene molecules. The rotational quantum numbers of these absorption lines and the nuclear spin isomers of ethylene molecules responsible for them are identified. (paper)
Infrared spectroscopy is a well-established method for identifying solid, liquid, and gas-phase chemicals. Accurate infrared spectroscopic analysis requires reference libraries where library endmembers reflect all optical phenomena contributing to the observed spectra. Traditional spectral libraries most often contain molecular-based absorption spectra, but these do not account for the complex scattering effects that become significant when measuring aerosols. In this work, we combine the laboratory-derived, wavelength-dependent complex optical vectors ( n / k ) of liquid dioctyl sebacate (DOS) with Mie scattering theory and the Beer–Lambert law to generate synthetic infrared transmission spectra of aerosolized DOS. Additionally, we record experimental infrared transmission spectra using an FTIR spectrometer coupled to a simple aerosol chamber filled with a quantified number size distribution of aerosolized DOS. The modeled and measured spectra show strong agreement, with Mie scattering effects clearly altering the overall spectral shape as well as the positions and profiles of absorption features. The results demonstrate that synthetic spectra generated from n / k values can reliably capture aerosol-specific spectral behavior and thus serve as a foundation for building scalable, physics-based aerosol reference libraries to enable infrared spectroscopic detection of aerosols.
We report the discovery of nonstellar hydrogen Balmer and metastable helium absorption lines accompanying a transient, high-velocity (0.05c) broad absorption line (BAL) system in the optical spectra of the tidal disruption event (TDE) AT2018zr (z = 0.071). In the Hubble Space Telescope UV spectra, absorption of high- and low-ionization lines is also present at this velocity, making AT2018zr resemble a low-ionization BALQSO. We conclude that these transient absorption features are more likely to arise in fast outflows produced by the TDE than absorbed by the unbound debris. In accordance with the outflow picture, we are able to reproduce the flat-topped Hα emission in a spherically expanding medium without invoking the typical prescription of an elliptical disk. We also report the appearance of narrow (∼1000 kms−1) N III λ4640, He II λ4686, Hα, and Hβ emission in the latetime optical spectra of AT2018zr, which may be a result of UV continuum hardening at late times, as observed by Swift. Including AT2018zr, we find a high association rate (three out of four) of BALs in the UV spectra of TDEs. This suggests that outflows may be ubiquitous among TDEs and less sensitive to viewing angle effects compared to QSO outflows.
We report the discovery of nonstellar hydrogen Balmer and metastable helium absorption lines accompanying a transient, high-velocity (0.05c) broad absorption line (BAL) system in the optical spectra of the tidal disruption event (TDE) AT2018zr (z = 0.071). In the Hubble Space Telescope UV spectra, absorption of high- and low-ionization lines is also present at this velocity, making AT2018zr resemble a low-ionization BALQSO. We conclude that these transient absorption features are more likely to arise in fast outflows produced by the TDE than absorbed by the unbound debris. In accordance with the outflow picture, we are able to reproduce the flat-topped Hα emission in a spherically expanding medium without invoking the typical prescription of an elliptical disk. We also report the appearance of narrow (~1000 kms(exp −1)) N III λ4640, He II λ4686, Hα, and Hβ emission in the late-time optical spectra of AT2018zr, which may be a result of UV continuum hardening at late times, as observed by Swift. Including AT2018zr, we find a high association rate (three out of four) of BALs in the UV spectra of TDEs. This suggests that outflows may be ubiquitous among TDEs and less sensitive to viewing angle effects compared to QSO outflows.
Infrared spectroscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter and Saturn -- and of Titan, the enigmatic satellite of Saturn. The 5 micron spectral region of these objects is transparent to deep levels, and is therefore particularly useful for the identification of molecules in the deep atmosphere at very low (parts per billion) concentrations. In 1991 we obtained data at J, H, K, and M and made repeated observations of Titan's albedo as the satellite orbited Saturn. The J albedo is 12 + -3% greater than the albedo measured in 1979; the H and K albedos are the same. There was no evidence for variations at any wavelength over the eastern half of Titan's orbit. We also obtained low resolution (R = 50) spectra of Titan between 3.1 and 5.1 microns. The spectra contain evidence for CO and CH3D absorptions. Spectra of Callisto and Ganymede in the 4.5 micron spectral region are featureless and give albedos of 0.08 and 0.04 respectively. If Titan's atmosphere is transparent near 5 microns, its surface albedo there is similar to Callisto's. In 1992 and 1993 we obtained further spectroscopic data of Titan with the UKIRT CGS4 spectrometer. We discovered two unexpected and unexplained spectral features in the 3-4 micron /spectrum of Titan. An apparent emission feature near the 3 micron (nu3) band of methane indicates temperatures higher than known to be present in Titan's upper stratosphere and may be caused by unexpected non-LTE emission. An absorption feature near 3.47 microns may be caused by absorption in solid grains or aerosol's in Titan's clouds. The feature is similar, but not identical to organics in the interstellar matter and in comets.
Infrared spectroscopy provides unique insights into the chemistry and dynamics of the atmospheres of Jupiter, Saturn, and Titan. In 1991 we obtained data at J, H, K, and M and made repeated observations of Titan's albedo as the satellite orbited Saturn. The J albedo is 12% +/- 3% greater than the albedo measured in 1979; the H and K albedos are the same. There was no evidence for variations at any wavelength over the eastern half of Titan's orbit. We also obtained low resolution (R=50) spectra of Titan between 3.1 and 5.1 microns. The spectra contain evidence for CO and CH3D absorptions. Spectra of Callisto and Ganymede in the 4.5 micron spectral region are featureless and give albedos of 0.08 and 0.04 respectively. If Titan's atmosphere is transparent near 5 microns, its surface albedo there is similar to Callisto's. In 1992 and 1993 we obtained further spectroscopic data of Titan with the UKIRT CGS4 spectrometer. We discovered two unexpected and unexplained spectral features in the 3-4 micron spectrum of Titan. An apparent emission feature near the 3 micron (nu sub 3) band of methane indicated temperatures higher than known to be present in Titan's upper stratosphere and may be caused by unexpected non-LTE emission. An absorption feature near 3.47 microns may be caused by absorption in solid grains or aerosols in Titan's clouds. The feature is similar but not identical to organics in the interstellar matter and in comets.
The ultraviolet (UV) absorption spectra were studied in UV–Vis–IR quartz glasses exposed to the rhenium ion irradiation at the energy of 30 keV. An increase in ion fluence (5 × 10{sup 15}–5 × 10{sup 17} cm{sup 2}) is found to result in a characteristic fan-shaped broadening of the optical absorption edge of glasses. The results were interpreted in the context of the generalized Urbach rule (the approximation of ion radiation induced quasi-dynamic disorder). The effective radiation disorder cross section of a glass matrix was evaluated from the dose dependence of characteristic Urbach energy. This parameter was found to vary between 1.07 × 10{sup –17}–1.2 × 10{sup –18} cm{sup 2} with increasing fluence. The optical gap width of implanted samples was estimated via the Tautz method for allowed direct interband transitions. The relationship between the second-order deformation potential constants, revealing the correlation between the Urbach energy and the optical gap width in a SiO{sub 2} quartz glass matrix was established using the equivalence principle of static and dynamic structural disorder.
We recently proposed Domain Separated Density Functional Theory (DS-DFT), a framework that allows for the combination of different levels of theory for the computation of the electronic structure of molecules. Here, this work discusses the application of DS-DFT to the computation of transition-state energy barriers and optical absorption spectra. We considered several hydrogen abstraction reactions and optical spectra of molecule/metal cluster systems, including the absorption of individual species such as carbon monoxide, methane, and molecular hydrogen to a Li6 cluster. We present and discuss two domain-separated methods: i), the screened-density approximation (SDA), and, ii), linearly weighted exchange (LWE). We find that SDA, which is applied as a hybridization based on atomic domains, could be useful to computing energy barriers, whereas LWE is suited for the analysis of electronic properties such as ground-state gaps, excitation energies, and oscillator strengths.
Layered Li-rich Ni, Mn, Co (NMC) oxide cathodes in Li-ion batteries provide high specific capacities (>250 mAh/g) via O-redox at high voltages. However, associated high-voltage interfacial degradation processes require strategies for effective electrode surface passivation. Here, we show that an acidic surface treatment of a Li-rich NMC layered oxide cathode material leads to a substantial suppression of CO 2 and O 2 evolution, ~90% and ~100% respectively, during the first charge up to 4.8 V vs. Li +/0 . CO 2 suppression is related to Li 2 CO 3 removal as well as effective surface passivation against electrolyte degradation. This treatment does not result in any loss of discharge capacity and provides superior long-term cycling and rate performance compared to as-received, untreated materials. We also quantify the extent of lattice oxygen participation in charge compensation (“O-redox”) during Li + removal by a novel ex-situ acid titration. Our results indicate that the peroxo-like species resulting from O-redox originate on the surface at least 300 mV earlier than the activation plateau region around 4.5 V. X-ray photoelectron spectra and Mn -L X-ray absorption spectra of the cathode powders reveal a Li + deficiency and a partial reduction of Mn ions on the surface of the acid-treated material. More interestingly, although the irreversible oxygen evolution is greatly suppressed through the surface treatment, our O K-edge resonant inelastic X-ray scattering shows the lattice O-redox behavior largely sustained. The acidic treatment, therefore, only optimizes the surface of the Li-rich material and almost eliminates the irreversible gas evolution, leading to improved cycling and rate performance. This work therefore presents a simple yet effective approach to passivate cathode surfaces against interfacial instabilities during high-voltage battery operation.
Pressure induced hydrogen collisions vibrational spectra absorption coefficients at high temperatures and local thermodynamic equilibrium
Data processing and calibration methods are described for tunable diode laser absorption spectrometers which produce harmonic absorption spectra as raw data for measuring gas mixing ratios down to parts-per-trillion levels at a variety of pressures. The methods, which take advantage of modern computer speed, memory, and data storage capabilities, are applicable to the detection of weakly absorbing gases in quantitative industrial monitoring, in addition to aircraft and balloon atmospheric measurements for which they were designed. Algorithms for calibration and data analysis, including rejection of erroneous spectra, variation of effective integration time, spectral alignment prior to averaging, and plotting and archiving of results, have been tested on actual stratospheric laser spectra recorded by the Aircraft Laser Infrared Absorption Spectrometer (ALIAS) spectrometer in numerous flights of NASA's ER-2 aircraft.
Platinum(II) π-extended porphyrins fused with pentacenequinone and dihydropentacene have been successfully synthesized. These porphyrins were investigated using various techniques including absorption, steady-state, and time-resolved phosphorescence spectroscopy and differential pulse voltammetry. UV–vis absorption spectra of pentacenequinone-fused porphyrins (SW-Pt1 and SW-Pt2) showed unusually broad and nontypical absorption patterns. Phosphorescence spectra of SW-Pt1, SW-Pt2, and SW-Pt3 displayed similar emissions in the 704–706 nm region indicating electronic transitions of similar origin; however, the triplet lifetimes were found to be quenched in the case of both SW-Pt1 and SW-Pt2, suggesting the occurrence of excited-state events. Facile reductions were obtained for both the pentacene-quinone-fused monomer (SW-Pt2) and dimer (SW-Pt1) and were identified to be located at the pentacenequinone components. Here, the observed orbital segregations for SW-Pt2 and SW-Pt1 from DFT calculations supported the possibility of charge transfer in these push–pull systems. Interestingly, the established energy level diagram revealed that the charge transfer from the triplet excited Pt porphyrin is thermodynamically an uphill process. Systematic studies involving both femtosecond and nanosecond transient absorption techniques revealed that the singlet excited Pt porphyrins undergo an intermediate charge transfer state prior to populating the triplet state, providing a plausible explanation for phosphorescence quenching. The lifetime of the intermediate charge transfer states was found to be 25.9 and 5.68 ps, respectively, for SW-Pt1 and SW-Pt2.
The source of the optical properties of natural melanin persists as an impressive conundrum, hindering a thorough comprehension of the complicated photo-protective contribution of these extensive natural pigments and the pragmatic design of revolutionary bioinspired materials for optoelectronic functionalities. Melanin is a natural pigment distributed in vivo, and provides protection from the sun rays, exhibiting a strong wide-band UV–visible absorption. In the present study, we investigated the optical properties of natural melanin at different pH concentrations within the framework of experimental techniques, namely, UV–visible absorption, Fourier transform infrared spectroscopy (FTIR), and fluorescence spectroscopies. The results indicate that the optical absorption and fluorescence of natural melanin are enhanced within the near-UV and visible regimes with an increase in the solution concentration, are dependent on the pH level, and can impact the emergence of a broad band of visible absorption. The variations in the optical absorption spectra of natural melanin solutions at various pH levels will demonstrate novel rational strategies for controlling their optical properties for potential optoelectronic applications.
The results of investigations of the optical-absorption spectra of bismuth-silicate (Bi{sub 12}SiO{sub 20}) single crystals are presented. The band-gap width and the characteristic Urbach energy are determined. The effect of preliminary X-ray irradiation on the behavior of the experimental spectral dependences and the values of the characteristic parameters induced by the bismuth-silicate defect structure is established.