mid-IR Spectra Research Articles

Geographical Traceability of Millet by Mid-Infrared Spectroscopy and Feature Extraction

To identify the geographical origin of millet accurately, 36 samples of Guangling millet, Qinzhouhuang millet, Liuseng millet, Qiananhuang millet, and 33 samples of Yuzhou millet were collected. Mid-infrared (mid-IR) spectra of all the samples were obtained. Denoising, standard normal variate (SNV), multiplicative scatter correction (MSC), and normalization were carried out to preprocess the data. Principal component analysis (PCA) was used to reduce the dimension of the data, combined with support vector machine (SVM), and the geographical origin of the five kinds of millet was identified. The recognition accuracy of the training set (99.2%) and the prediction set (98.3%) were highest when using the first 12 principal components, indicating that the established mid-IR spectroscopic identification model was feasible and effective. PCA, window analysis, hierarchical clustering analysis, and SVM were combined to extract the feature information of mid-IR spectra of millet from five producing areas. Five wavenumbers, 1026, 1053, 1685, 1715, and 1744 cm-1, were found to be with small correlation, and the recognition accuracy of the training set and the prediction set based on these five features were 95.8% and 100.0%, respectively. The feature extraction method established here could be used to improve the prediction efficiency of the identification model and provide data support for the analysis of differential components.

Reactive CaCO3 Formation from CO2 and Methanolic Ca(OH)2 Dispersions: Transient Methoxide Salts, Carbonate Esters and Sol-Gels.

A combination of ex situ and in situ characterization techniques was used to determine the mechanism of calcium carbonate (CaCO3) formation from calcium hydroxide (Ca(OH)2) dispersions in methanol/water (CH3OH/H2O) systems. Mid-infrared (mid-IR) analysis shows that in the absence of carbon dioxide (CO2) Ca(OH)2 establishes a reaction equilibrium with CH3OH, forming calcium hydroxide methoxide (Ca(OH)(OCH3)) and calcium methoxide (Ca(OCH3)2). Combined ex situ mid-IR, thermogravimetric analysis (TGA), X-ray diffraction (XRD), X-ray absorption spectroscopy and scanning electron microscopy examination of the reaction product formed in the presence of CO2 reveals the formation of calcium dimethylcarbonate (Ca(OCOOCH3)2). This strongly suggests that carbonation takes place by reaction with the Ca(OCH3)2 formed from a Ca(OH)2 and CH3OH reaction. Time-resolved XRD indicates that in the presence of H2O the Ca(OCOOCH3)2 ester releases CH3OH and CO2, forming ACC, which subsequently transforms into vaterite and then calcite. TGA reveals that thermal decomposition of Ca(OCOOCH3)2 in the absence of H2O mainly leads to the reformation of Ca(OCH3)2, but this is accompanied by a significant parallel reaction that releases dimethylether (CH3OCH3) and CO2. CaCO3 is the final product in both decomposition pathways. For CH3OH/H2O mixtures containing more than 50 mol % H2O, direct formation of calcite from Ca(OH)2 becomes the dominant pathway, although the formation of some Ca(OCOOCH3)2 was still evident in the in situ mid-IR spectra of 20 and 40 mol % CH3OH systems. In the presence of ≤20 mol % H2O, hydrolysis of the ester led to the formation of an ACC sol-gel. In both the 90 and 100 mol % CH3OH systems, diffusion-limited ACC → vaterite → calcite transformations were observed. Traces of aragonite were also detected. We believe that this is the first time that these reaction pathways during the carbonation of Ca(OH)2 in a methanolic phase have been systematically and experimentally characterized.

Mid-Infrared Spectrometer Based on Tunable Photoresponses in Pdse2

Mid-infrared (mid-IR) photodetection is important for various applications, including biomedical diagnostics, security, chemical identification, and free-spacing optical communications. However, conventional “photon” mid-IR photodetectors require liquid nitrogen cooling (i.e., MCT). Furthermore, acquiring mid-IR spectra usually involves a complex and expensive Fourier Transform Infrared spectrometer, a tabletop instrument consisting of a meter-long interferometer and MCT detectors, which is not suitable for mobile and compact device applications. In this work, we present tunable photoresponsivity in the mid-IR wavelength in palladium diselenide (PdSe2) – molybdenum disulfide (MoS2) heterostructure field-effect transistors (FETs), operating at room temperature. Furthermore, we applied a tunable membrane cavity to modulate the Fabry–Pérot resonance to modulate the absorption spectrum of the device layer. We used a robust polyetherimide (PEI) membrane with CVD-grown graphene to electrically tune the membrane structure. For the next step, we will integrate the PdSe2-based photodetector and tunable membrane to increase detection sensitivity and spectrum tunability to realize the ‘learning’-based spectroscopy.

Exploring the Scaling Factors for Infrared Modes of PANHs - A Case Study on Cationic 3-Azafluoranthene⋅+ and Protonated 3-Azafluoranthene.

Infrared (IR) emission bands by interstellar polycyclic aromatic hydrocarbons (PAHs) and polycyclic aromatic nitrogen heterocycles (PANHs) are observed towards a large variety of interstellar objects and offer detailed insights into the chemistry and physics of the interstellar medium. The analysis of the emission bands, and thus the interpretation of the molecular characteristics of the carriers, heavily relies on the use of density functional theory (DFT) calculated IR spectra. However, there are significant challenges in accurately predicting the experimental IR band positions, particularly for PANH emission vibrational modes around 6 μm. In this work, we present gas-phase mid-infrared (mid-IR) spectra of cationic 3-azafluoranthene (3AF⋅+) and protonated 3-azafluoranthene (3AFH+) to investigate their experimental IR band positions in relation to DFT calculated bands. The experimental spectra are compared to DFT simulated spectra, where different approaches were followed to correct for anharmonicities. The best agreement is achieved by scaling frequencies of modes with large nitrogen displacements with a different factor. Even though our findings might be limited to a small number of PANH structures, they indicate, that nitrogen atom incorporation needs to be accounted for by carefully adjusting the corresponding scaling factors while computing IR spectra of PANHs on DFT level.

JOYS: MIRI/MRS spectroscopy of gas-phase molecules from the high-mass star-forming region IRAS 23385+6053

Context. Space-based mid-infrared (IR) spectroscopy is a powerful tool for the characterization of important star formation tracers of warm gas which are unobservable from the ground. The previous mid-IR spectra of bright high-mass protostars with the Infrared Space Observatory (ISO) in the hot-core phase typically show strong absorption features from molecules such as CO2, C2H2, and HCN. However, little is known about their fainter counterparts at earlier stages. Aims. We aim to characterize the gas-phase molecular features in James Webb Space Telescope Mid-Infrared Instrument Medium Resolution Spectrometer (MIRI/MRS) spectra of the young and clustered high-mass star-forming region IRAS 23385+6053. Methods. Spectra were extracted from several locations in the MIRI/MRS field of view, targeting two mid-IR sources tracing embedded massive protostars as well as three H2 bright outflow knots at distances of >8000 au from the multiple. Molecular features in the spectra were fit with local thermodynamic equilibrium (LTE) slab models, with their caveats discussed in detail. Results. Rich molecular spectra with emission from CO, H2, HD, H2O, C2H2, HCN, CO2, and OH are detected towards the two mid-IR sources. However, only CO and OH are seen towards the brightest H2 knot positions, suggesting that the majority of the observed species are associated with disks or hot core regions rather than outflows or shocks. The LTE model fits to 12CO2, C2H2, HCN emission suggest warm 120–200 K emission arising from a disk surface around one or both protostars. The abundances of CO2 and C2H2 of ~10−7 are consistent with previous observations of high-mass protostars. Weak ~500 K H2O emission at ~6–7 µm is detected towards one mid-IR source, whereas 250–1050 K H2O absorption is found in the other. The H2O absorption may occur in the disk atmosphere due to strong accretion-heating of the midplane, or in a disk wind viewed at an ideal angle for absorption. CO emission may originate in the hot inner disk or outflow shocks, but NIRSpec data covering the 4.6 µm band head are required to determine the physical conditions of the CO gas, as the high temperatures seen in the MIRI data may be due to optical depth. OH emission is detected towards both mid-IR source positions and one of the shocks, and is likely excited by water photodissociation or chemical formation pumping in a highly non-LTE manner. Conclusions. The observed molecular spectra are consistent with disks having already formed around two protostars in the young IRAS 23385+6054 system. Molecular features mostly appear in emission from a variety of species, in contrast to the more evolved hot core phase protostars which typically show only absorption; however, further observations of young high-mass protostars are needed to disentangle geometry and viewing angle effects from evolution.

IR spectra of cationic 1,5,9-triazacoronene and two of its cationic derivatives.

Infrared emission features are observed towards diverse astronomical objects in the interstellar medium (ISM). Generally, the consensus is that these IR features originate from polycyclic aromatic hydrocarbons (PAHs) and are hence named aromatic infrared bands (AIBs). More recently, it has been suggested that nitrogen substituted PAHs (PANHs) contribute to the AIBs as well and it has even been shown that nitrogen inclusion in PAHs can improve the match with the AIBs, specifically around the 6.2 μm feature. In order to determine which specific molecules or functional groups are at the origin of the AIBs, IR spectra of various PA(N)Hs are experimentally and computationally studied. In this work we expand on the spectroscopic investigation of PANHs by presenting the gas-phase mid-IR spectra of 1,5,9-triazacoronene˙+ (TAC˙+, m/z 303), a threefold nitrogenated congener of coronene˙+, its protonated derivative TACH+ (m/z 304) and the product that forms when water adds to dehydrogenated TAC˙+[TAC-H + H2O]+ (m/z 320). We analyze the mid-IR spectra by comparing them with vibrational modes calculated at the B3LYP/6-311++G(d,p) level a theory and we present a possible geometry for [TAC-H + H2O]+. The TAC˙+ mid-IR spectrum is compared to that of coronene˙+ and is demonstrated to be remarkably similar. We put TAC˙+ and TACH+ into astronomical context by comparing their recorded mid-IR spectra to observed ISM spectra of four spectral classes. From this we conclude that TAC˙+ and TACH+ could both contribute to the AIBs, with TACH+ being a more likely contributor than TAC˙+.

Infrared Spectral Fingerprint of Neutral and Charged Endo- and Exohedral Metallofullerenes

Small metal-containing molecules have been detected and recognized as one of the hybrid species that are efficiently formed in space, especially in the circumstellar envelopes of evolved stars. It has also been predicted that more complex hybrid species such as those formed by metals and fullerenes (metallofullerenes) could be present in these circumstellar environments. Recently, quantum-chemical simulations of metallofullerenes have shown that they are potential emitters contributing to the observed mid-IR spectra in the fullerene-rich circumstellar environments of different types of evolved stars. Here we present the individual simulated mid-IR (∼5–50 μm) spectra of 28 metallofullerene species. Both neutral and charged endo- and exohedral metallofullerenes for seven different metals (Li, Na, K, Ca, Mg, Ti, and Fe) have been considered. The changes induced by the metal–C60 interaction in the intensity and position of the spectral features are highlighted using charge-density difference maps and electron-density partitioning. Our calculations identify the fundamental IR spectral regions in which, depending on the metal binding nature, there should be a major spectral contribution from each of the metallofullerenes. The IR spectra of the metallofullerenes are made publicly available to the astronomical community, especially users of the James Webb Space Telescope, for comparisons that could eventually lead to the detection of these species in space.

Mid-infrared photocurrent nano-spectroscopy exploiting the thermoelectric effect in graphene

We develop a conductive-atomic force microscope coupled to a mid-infrared (IR) quantum cascade laser that allows to measure mid-IR photocurrent maps and spectra with nanometric spatial resolution. Here, we exploit the photo-induced thermoelectric effect of graphene to obtain the mid-IR local absorption spectra of nanoscale devices and materials. By scanning the probe in AFM-contact mode, the thermoelectric photocurrent can be mapped throughout the graphene layer, which acts as a semitransparent transducer. At zero voltage bias applied to the probe tip, we observe very low noise (about 25 pA/Hz), which makes our technique competitive with others in measuring the local IR absorption in nanomaterials with insufficient thermal expansion coefficient, or to characterize nanoscale devices that significantly absorb IR radiation, such as mid-infrared photodetectors.

The IR Compactness of Dusty Galaxies Sets Star Formation and Dust Properties at z ∼ 0–2

The surface densities of gas, dust, and stars provide a window into the physics of star formation that, until the advent of high-resolution far-IR/submillimeter observations, has been historically difficult to assess among dusty galaxies. To study the link between IR surface densities and dust properties, we leverage the Atacama Large Millimetre/Submillimetre Array archive to measure the extent of cold dust emission in 15 z ∼ 2 IR-selected galaxies selected on the basis of having available mid-IR spectroscopy from Spitzer. We use the mid-IR spectra to constrain the relative balance between dust heating from star formation and active galactic nuclei (AGNs), and to measure emission from polycylic aromatic hydrocarbons (PAHs), small dust grains that play a key role in the photoelectric heating of gas. In general, we find that dust-obscured star formation at high IR surface densities exhibits similar properties at low and high redshift, namely, local luminous IR galaxies (LIRGs) have comparable PAH luminosity to total dust mass ratios as high-z galaxies, and star formation at z ∼ 0–2 is more efficient at high IR surface densities despite the fact that our sample of high-z galaxies is closer to the main sequence than local LIRGs. High star formation efficiencies are coincident with a decline in the PAH-to-IR luminosity ratio reminiscent of the deficit observed in far-IR fine-structure lines. Changes in the gas and dust conditions arising from high star formation surface densities might help drive the star formation efficiency up. This could help explain the high efficiencies needed to reconcile star formation and gas volume densities in dusty galaxies at cosmic noon.

Short communication: Predicting blood plasma non-esterified fatty acid and beta-hydroxybutyrate concentrations from cow milk-addressing systematic issues in modelling.

Negative energy status in early lactation is linked to a variety of metabolic disorders, reduced fertility, and decreased milk production. To improve the energy status of cows by breeding and management, the identification of negative energy status is crucial. While biomarkers such as non-esterified fatty acid (NEFA) concentration and beta-hydroxybutyrate (BHB) in blood plasma could be used to identify a negative energy state, measuring them directly from blood is both invasive and expensive. In this work, we developed prediction equations for blood plasma NEFA and BHB levels based on mid-IR spectral measurements of milk. The models were fitted using partial least squares regression and evaluated using both cross-validation and independent-herd validation. A total of 3183 spectral records from 606 lactations originating from three different herds were utilised. R2 values of 0.53 (RMSE=0.206mmol/l, RMSE of cross-validation (RMSECV) 0.217mmol/l) for NEFA and 0.63 (RMSE=0.326mmol/l, RMSECV=0.353mmol/l) for BHB were obtained. Furthermore, relatively similar prediction accuracies were found for BHB (RMSE of prediction (RMSEP) 0.411mmol/l and 0.422mmol/l) and NEFA (RMSEP=0.186mmol/l and 0.221mmol/l) when model training was done using two herds and validated on the third herd. The results from the model fits confirm that it is possible to build blood plasma BHB and NEFA models based on mid-IR spectra that are sufficiently accurate for practical use.

The hunt for formamide in interstellar ices

Context. Although solid-state pathways are expected to dominate the formation mechanisms of many complex organic molecules (COMs), very few COMs have been securely identified in interstellar ices, in stark contrast with the many COM detections in the gas phase. The launch of the James Webb Space Telescope (JWST) and its increase in sensitivity and spectral resolution opens the possibility of identifying more COMs in ices, but additional laboratory data are necessary. Formamide (NH2CHO) is one such COM that is of great interstellar and prebiotic relevance where more laboratory data are needed in the hunt for its presence in interstellar ices. Aims. This work aims to characterize the mid-IR spectra of formamide in its pure form as well as in mixtures of the most abundant interstellar ices via laboratory simulation of such ices, as well as to demonstrate how these laboratory spectra can be used to search for formamide in ice observations. Methods. Mid-IR spectra (4000–500 cm−1/2.5–20 μm) of formamide, both in its pure form as well as in binary and tertiary mixtures with H2O, CO2, CO, NH3, CH3OH, H2O:CO2, H2O:NH3, CO:NH3, and CO:CH3OH, were collected at temperatures ranging from 15–212 K. Results. Apparent band strengths and positions of eight IR bands of pure amorphous and crystalline formamide at various temperatures are provided. Three of these bands are identified as potential formamide tracers in observational ice spectra: the overlapping C = O stretch and NH2 scissor bands at 1700.3 and 1630.4 cm−1 (5.881 and 6.133 μm), the CH bend at 1388.1 cm−1 (7.204 μm), and the CN stretch at 1328.1 cm−1 (7.529 μm). The relative apparent band strengths, positions, and full width half maxima (FWHM) of these features in mixtures at various temperatures were also determined. All of the laboratory spectra are available to the community on the Leiden Ice Database for Astrochemistry (LIDA) for use in the interpretation of both observations (e.g., from JWST) and laboratory spectroscopic data. Finally, the laboratory spectra are compared to observational spectra of a variety of low- and high-mass young stellar objects as well as prestellar cores observed with the Infrared Space Observatory, the Spitzer Space Telescope, and JWST. A comparison between the formamide CH bend in laboratory data and the 7.24 μm band in the observations tentatively indicates that, if formamide ice is contributing significantly to the observed absorption, it is more likely in a polar matrix. Upper limits ranging from 0.35-5.1% with respect to H2O were calculated via scaling the formamide:H2O laboratory spectrum to the observations. These upper limits are in agreement with gas-phase formamide abundances and take into account the effect of a H2O matrix on formamide’s band strengths.

Spectral prediction of soil salinity and alkalinity indicators using visible, near-, and mid-infrared spectroscopy

Drought and the impacts of climate change have led to an escalation in soil salinity and alkalinity across various regions worldwide, including Iran. The Chahardowli Plain in western Iran, in particular, has witnessed a significant intensification of this phenomenon over the past decade. Consequently, modeling of soil attributes that serve as indicators of soil salinity and alkalinity became a priority in this region. To date, only a limited number of studies have been conducted to assess indicators of salinity and alkalinity through spectrometry across diverse spectral ranges. The spectral ranges encompassing mid-infrared (mid-IR), visible, and near-infrared (vis-NIR) spectroscopy were employed to estimate soil properties including sodium adsorption ratio (SAR), exchangeable sodium ratio (ESR), exchangeable sodium percentage (ESP), pH, and electrical conductivity (EC). Five distinct models were employed: Partial Least Squares Regression (PLSR), bootstrapping aggregation PLSR (BgPLSR), Memory-Based Learning (MBL), Random Forest (RF), and Cubist. The calibration and assessment of model performance were carried out using several key metrics including Ratio of Performance to Deviation (RPD) and the coefficient of determination (R2). Analysis of the outcomes indicates that the accuracy and precision of the mid-IR spectra surpassed that of vis-NIR spectra, except for pH, which exhibited a superior RPD compared to other properties. Notably, in the prediction of pH utilizing vis-NIR reflectance spectra, the BgPLSR model exhibited the highest accuracy and precision, boasting an RPD value of 2.56. In the domain of EC prediction, the PLSR model yielded an RPD of 2.64. For SAR, the MBL model achieved an RPD of 2.70, while ESR prediction benefited from the MBL model with an impressive RPD of 4.36. Likewise, the MBL model demonstrated remarkable precision and accuracy in ESP prediction, garnering an RPD of 4.41. The MBL model's efficacy in forecasting with limited datasets was notably pronounced among the models considered. This study underscores the valuable role of spectral predictions in facilitating the work of soil surveyors in gauging salinity and alkalinity indicators. It is recommended that the integration of spectrometry-based salinity and alkalinity predictions be incorporated into forthcoming soil mapping endeavors within semi-arid and arid regions.

Graph Theoretical Analysis of local ultraluminous infrared galaxies and quasars

We present a methodological framework for studying galaxy evolution by utilizing Graph Theory and network analysis tools. We study the evolutionary processes of local ultraluminous infrared galaxies (ULIRGs) and quasars and the underlying physical processes, such as star formation and active galactic nucleus (AGN) activity, through the application of Graph Theoretical analysis tools. We extract, process and analyze mid-infrared spectra of local (z ¡ 0.4) ULIRGs and quasars between 5-38μm through internally developed Python routines, in order to generate similarity graphs, with the nodes representing ULIRGs being grouped together based on the similarity of their spectra. Additionally, we extract and compare physical features from the mid-IR spectra, such as the polycyclic aromatic hydrocarbons (PAHs) emission and silicate depth absorption features, as indicators of the presence of star-forming regions and obscuring dust, in order to understand the underlying physical mechanisms of each evolutionary stage of ULIRGs. Our analysis identifies five groups of local ULIRGs based on their mid-IR spectra, which is quite consistent with the well established fork classification diagram by providing a higher level classification. We demonstrate how graph clustering algorithms and network analysis tools can be utilized as unsupervised learning techniques for revealing direct or indirect relations between various galaxy properties and evolutionary stages, which provides an alternative methodology to previous works for classification in galaxy evolution. Additionally, our methodology compares the output of several graph clustering algorithms in order to demonstrate the best-performing Graph Theoretical tools for studying galaxy evolution.

Visible and infrared spectra of the solids α- and β-O2 at 9–30 K

ABSTRACT To establish the spectroscopy of the solids α- and β-oxygen, we measured the thermal ramping spectra of the solid O2 in visible and near-infrared (near-IR) wavelength range 450–1020 nm and mid-infrared (mid-IR) range 500–5000 cm−1 (2–20 μm) at temperature 9–30 K. Besides the solids α- and β-oxygen, the imperfect structure of O2 ice might co-exist at low temperature. In mid-IR spectra, a triplet was observed at 1545.7, 1548.1, and 1549.6 cm−1 associated to the imperfect crystallinity of solid O2; the triplet existed below 27 K, but not at 30 K and on re-cooling to 9 K. The spectra measured at re-cooled 9 and 30 K are evidently responsible only for the solids α- and β-O2, respectively; overall, the spectra of the solids α- and β-O2 appear similar in the visible region, but those differ significantly from the spectrum of the solid O2 contaminated with imperfect structure. For solid α-O2, IR lines were recorded at 1591 and 1617 cm−1, which exhibited a reversible behaviour through the α-β phase transition temperature at 24 K. The visible spectrum of the separate solid α-O2 was obtained for the first time.

Nuclear high-ionisation outflow in the Compton-thick AGN NGC 6552 as seen by the JWST mid-infrared instrument

Context. During the commissioning of the James Webb Space Telescope (JWST), the mid-infrared instrument (MIRI) observed NGC 6552 with the MIRI Imager and the Medium-Resolution Spectrograph (MRS). NGC 6552 is an active galactic nucleus (AGN) at a redshift of 0.0266 (DL = 120 Mpc) classified as a Seyfert 2 nucleus in the optical and Compton-thick AGN in the X-ray. Aims. This work exemplifies and demonstrates the MRS capabilities to study the mid-infrared (mid-IR) spectra and characterise the physical conditions and kinematics of the ionised and molecular gas in the nuclear regions of nearby galaxies. Methods. MIRI Imager observations covers the full NGC 6552 galaxy at 5.6 μm. MRS observations covers its nuclear region (3.6×4.3 kpc at 17.7–27.9 μm) in a wavelength range between 4.9 and 27.9 μm. These observations were obtained with the aim to investigate the persistence of the MIRI detectors (residual signal left from previous bright source observations). However, NGC 6552 observations demonstrate the performance and power of the MIRI instrument even with a non-optimal observational strategy. Results. We obtained the nuclear, circumnuclear, and central mid-IR spectra of NGC 6552. They provide the first clear observational evidence for a nuclear outflow in NGC 6552. The outflow contributes to 67±7% of the total line flux independent of the ionisation potential (27–187 eV) and critical densities (104–4×106 cm−3), showing an average blue-shifted peak velocity of −127±45 km s−1 and an outflow maximal velocity of 698±80 km s−1. Since the mid-IR photons penetrate dusty regions as efficiently as X-ray keV photons, we interpret these results as the evidence for a highly ionised, non-stratified, AGN-powered, and fast outflowing gas in a low density environment (few 103 cm−3) located very close (< 0.2 kpc) to the Compton-thick AGN. Nine pure rotational molecular Hydrogen lines are detected and spectrally resolved, and exhibit symmetric Gaussian profiles, consistent with the galactic rotation, and with no evidence of outflowing H2 material. We detect a warm H2 mass of 1.9 ± 1.1 × 107 M⊙ in the central region (1.8 kpc in diameter) of the galaxy, with almost 30% of that mass in the circumnuclear region. Line ratios confirm that NGC 6552 has a Seyfert nucleus with a black hole mass estimated in the range of 0.6–6 million solar masses. Conclusions. This work demonstrates the power of the newly commissioned MIRI Medium Resolution Spectrograph to reveal new insights in the kinematics and ionisation state of the interstellar medium around the dusty nuclear regions of nearby active galaxies.

The First JWST Spectrum of a GRB Afterglow: No Bright Supernova in Observations of the Brightest GRB of all Time, GRB 221009A

We present James Webb Space Telescope (JWST) and Hubble Space Telescope (HST) observations of the afterglow of GRB 221009A, the brightest gamma-ray burst (GRB) ever observed. This includes the first mid-IR spectra of any GRB, obtained with JWST/Near Infrared Spectrograph (0.6–5.5 micron) and Mid-Infrared Instrument (5–12 micron), 12 days after the burst. Assuming that the intrinsic spectral slope is a single power law, with F ν ∝ ν −β , we obtain β ≈ 0.35, modified by substantial dust extinction with A V = 4.9. This suggests extinction above the notional Galactic value, possibly due to patchy extinction within the Milky Way or dust in the GRB host galaxy. It further implies that the X-ray and optical/IR regimes are not on the same segment of the synchrotron spectrum of the afterglow. If the cooling break lies between the X-ray and optical/IR, then the temporal decay rates would only match a post-jet-break model, with electron index p < 2, and with the jet expanding into a uniform ISM medium. The shape of the JWST spectrum is near-identical in the optical/near-IR to X-SHOOTER spectroscopy obtained at 0.5 days and to later time observations with HST. The lack of spectral evolution suggests that any accompanying supernova (SN) is either substantially fainter or bluer than SN 1998bw, the proto-type GRB-SN. Our HST observations also reveal a disk-like host galaxy, viewed close to edge-on, that further complicates the isolation of any SN component. The host galaxy appears rather typical among long-GRB hosts and suggests that the extreme properties of GRB 221009A are not directly tied to its galaxy-scale environment.

Mid-IR absorption spectra of C1-C4 alkyl acetates at high temperatures

We present measurements of the temperature-dependent absorption cross-section of C1-C4 alkyl acetates (methyl acetate, ethyl acetate, n-propyl acetate, n‑butyl acetate) covering their strongest infrared absorption band near 1250 cm−1. The methodology employed here consists of a broadband rapid-tuning MIRcat-QT™ laser in conjunction with a shock tube. The spectral measurements were performed over the wavelength range of 7.52 – 8.62 μm (1160 – 1330 cm−1), temperatures of 580 – 980 K, and pressures near 1.3 bar. The reported IR spectra are the first experimental measurements of the high-temperature absorption spectra of these species, and the measured spectra showed strong temperature dependence. We provide herein absorption cross-section correlations for a wide range of spectra and a wide range of temperatures. Rapid measurements of alkyl acetate in transient environments may be performed in a fixed-wavelength mode by choosing a suitable wavelength. Based on our analysis, we propose a wavelength of 1221.27 cm−1 which exhibited minimal temperature and pressure dependence over the range of investigated conditions. We utilized this strategy for measuring methyl acetate concentration during its high-temperature pyrolysis.

Spectroscopic investigation of interstellar hydrogenated carbon clusters

Context. The assignment of the mid-infrared (mid-IR) emission features and plateaus observed in C-rich and H-rich regions of the interstellar medium (ISM) is still debated. Such mid-IR assignments must also be related to their contribution to the extinction curve in our galaxy and to the ultraviolet (UV) bump. Aims. The aim of this work is to investigate the influence of hydrogenation rate on the mid-IR spectra of populations of carbon clusters in order to constraint the nH/nC ratios in regions of the ISM where carbon is an important component. Their potential contribution to the extinction curve and in particular to the UV bump is also investigated. Methods. The absorption IR and optical spectra of tens of thousands of C24Hn (n = 0, 6, 12, 18, 24) isomers classified into structural families – namely flakes, branched, pretzels, and cages – were computed using the density functional based tight binding electronic structure method and its time-dependent version, respectively. Final spectra were obtained by averaging the spectra of many individual isomers. Results. The shapes and the relative intensities of the bands centered at ~3.25 and 3.40 µm and assigned to the C–H stretch of sp2 and sp3 carbon atoms, respectively, present a clear dependence on the nH/nC ratio. From a comparison with the astronomical spectrum from the Orion bar H2S1, the most interesting emitting candidates would pertain to the flakes population; this is the most energetically favorable family of clusters, possessing a high content of five and six carbon rings and being mostly planar, with no sp1 carbon atoms and with a nH/nC ratio of lower than 0.5. The same conclusion is drawn when comparing the computed IR features in the [4–20 µm] region with the observed plateaus from some C-rich and H-rich planetary nebulae objects of the Small Magellanic Cloud. The contribution of the same family could be considered for the UV bump. When nH/nC increases, only a contribution to the high-energy part of the continuum due to σ → π✶ excitations can reasonably be considered. Conclusions. These results bring some constraints on the structural features and on the nH/nC ratio of the hydrogenated carbon populations emitting in the mid-IR domain in interstellar objects such as protoplanetary and reflection nebulae. The flakes population, with a low nH/nC ratio, is an interesting candidate for the carbon population emitting in these regions, but not for that absorbing in the diffuse ISM. None of the populations studied in the present work can account for the UV bump, but they would contribute to a broad extinction rise in this domain. The computed features reported in this article could be used to interpret future astronomical data provided by the James Webb Space Telescope.

Laboratory IR spectroscopy of soils from Apollo 14, 15, and 16: Spectral parameters and maturity

Sieved size fractions (0–25 ​μm, 25–63 ​μm, 63–125 ​μm, and 125–250 ​μm) and bulk (unsieved) material from lunar soils from Apollo 14 (14163,135 and14259,672), Apollo 15 (15101,319 and 15401,147), and 16 (61220,41, 62231,55 and 67481,96) were analyzed in diffuse reflectance in the mid-infrared (3–18 ​μm). These soils reflect formation in a range of geological settings including basalt protoliths (Apollo 15), and feldspathic impact ejecta protoliths (Apollo 14 and Apollo 16). Mid-IR spectra analyses were made with the same samples using broad spot analyses using a diffuse reflectance set up, and by micro-FTIR under low vacuum and ambient laboratory conditions. Comparison of the data generated by the Broad Spot and micro-FTIR Techniques shows only minor differences in terms of both band positions and relative intensities.

Importance of laboratory experimental studies of silicate grains for exoplanet atmosphere characterization

The study of exoplanetary atmospheres extends the frontiers of astronomy, astrophysics, and astrochemistry. Moreover, studies of exoplanets as being linked to the search for extraterrestrial life and other habitable planets are of interest not only for scientists, but for a much wider public audience. There is much evidence that clouds exist and are common in the exoplanetary atmospheres at high temperatures. Their origin can be gas-phase condensation of silicate materials and other refractory materials. Clouds have a major impact on the planets’ observable properties. Models describing atmospheres of exoplanets and brown dwarfs point to the necessity of including nanometer-to micrometer-sized grains of silicates. Observational mid-IR spectra have also provided tentative evidence of silicate grain absorption. Thus, silicates seem to be the first target for future astronomical observations of cloudy atmospheres and for laboratory studies supporting these observations. However, high-temperature laboratory studies of optical and structural properties of refractory materials, including silicates, and of gas-grain and grain surface chemistry needed for the decoding of astronomical spectra and for the development of reliable atmospheric models present practically uncharted territory. The aim of our paper is to review previous studies of optical and chemical properties of silicate materials and to emphasize the importance and perspective of high-temperature measurements of laboratory analogues of atmospheric silicate grains for exoplanet atmosphere characterization. This is particularly important in the light of new advanced astronomical instruments, which, as we expect, will bring comprehensive information on exoplanetary atmospheres.