Band Positions Research Articles

Central Ring Puckering Enhances the Stokes Shift of Xanthene Dyes.

Small-molecule dyes are generally designed based on well-understood electronic effects. However, steric hindrance can promote excited-state geometric relaxation, increasing the difference between the positions of absorption and emission bands (the Stokes shift). Accordingly, we hypothesized that sterically induced central ring puckering in xanthene dyes could be used to systematically increase their Stokes shift. Through a combined experimental/quantum-chemical approach, we screened a group of (9-acylimino)-pyronin dyes with a perturbed central ring geometry. Our results showed that an atom with sp3 hybridization in position 10 of (9-acylimino)-pyronins induces central ring puckering and facilitates excited-state geometric relaxation, thereby markedly enhancing their Stokes shifts (by up to ~2000 cm-1). Thus, we prepared fluorescent (9-acylimino)-pyronin pH sensors, which showed a Stokes shift disparity between acid and base forms of up to ~8700 cm-1. Moreover, the concept of ring puckering-enhanced Stokes shift can be applied to a wide range of xanthene analogues found in the literature. Therefore, central ring puckering may be reliably used as a strategy for enhancing Stokes shifts in the rational design of dyes.

Phytochemical Investigation of Tecoma capensis Flower Aqueous Extract and In Vitro Biological Studies: Anti‐Bacterial and Anti‐Proliferative Activities of its Silver Nanoparticles

AbstractIn this study, we report the synthesis of silver nanoparticles (AgNPs) from Tecoma capensis flower aqueous extract (TcAqFE). The impact of AgNPs on microstructural, optical, antibacterial and antiproliferative properties have been investigated through UV‐visible spectroscopy, X‐ray diffraction, transmission electron microscopy (TEM), fourier infra‐red spectroscopy (FTIR), agar well diffusion technique assay and MTT. The particles size estimated from TEM and XRD is in the range of 1–10 nm. The XRD pattern reveals that the Tecoma capensis silver nanoparticles (TcAgNPs) have a cubic crystal structure. FTIR spectra showed band positions at 1071, 1358, 1620, 1962, 2150, 2920 and 3361 cm−1. Surface plasmon resonance (SPR) in AgNPs became evident with an absorption peak at 407 nm. GC‐MS analysis of ethanolic flower extract revealed the presence of major phytochemical constituents, including Butanal (57.14 %), Propanol (20.23 %), Ethanone (4.88 %), Mesitylene (3.70 %), Hexanal (3.33 %), 4‐Cyclopentene‐1,3‐diol, trans (3.16 %), Furan (2.94 %), 5‐Hepten‐2‐one (2.58 %), and Acetic acid (1.68 %). The antibacterial assay results clearly indicate that the TcAgNPs exhibited the maximum activity against Salmonella typhi, with inhibition zone (IZ) values of (40±1.4 mm), followed by Bacillus subtilis (35.66±2.0 mm), Staphylococcus aureus (32.6±0.64 mm), Escherichia. coli (29.66±2.05 mm), Listeria monocytogenes (27±1.63 mm), and Klebsiella pneumoniae exhibiting the least IZ values (23±1.6 mm). Minimum inhibitory concentration (MIC) values ranged from 0.20 to 2.81 mg/mL. The highest MIC value 2.81 mg/mL was observed in case of Salmonella typhi, while Staphylococcus aureus (0.20 mg/mL), displayed the lowest MIC values. The MIC of Gentamycin also ranged from 0.012 to 0.024 mg/mL. MTT assay demonstrated that the aqueous extract was potent against the cancer cell line A549, with a GI50 of 71.79 μg/mL. These results suggest that TcAgNPs have therapeutic potential and can serve as antibacterial and antiproliferative agents to protect against several ailments.

Iron Complexes as Potential Carriers of Diffuse Interstellar Bands: The Photodissociation Spectrum of Fe+(H2O) at Optical Wavelengths.

The fullerene ion C60+ is the only carrier of diffuse interstellar bands (DIBs) identified so far. Transition-metal compounds feature electronic transitions in the visible and near-infrared regions, making them potential DIB carriers. Since iron is the most abundant transition metal in the cosmos, we here test this idea with Fe+(H2O). Laboratory spectra were obtained by photodissociation spectroscopy at 80 K. Spectra were modeled with the reflection principle. A high-resolution spectrum of the DIB standard star HD 183143 served as an observational reference. Two broad bands were observed from 4120 to 6800 Å. The 4120-4800 Å band has sharp features emerging from the background, which have the width of DIBs but do not match the band positions of the reference spectrum. Calculations show that the spectrum arises from a d-d transition at the iron center. While no match was found for Fe+(H2O) with known DIBs, the observation of structured bands with line widths typical for DIBs shows that small molecules or molecular ions containing iron are promising candidates for DIB carriers.

Isotopic effect of oxygen on the Raman mapping of a polycrystalline uranium dioxide UO2

AbstractUranium dioxide (UO2) is a widely studied material due to its use as fuel in pressurised water reactors (PWR), and Raman spectroscopy is a technique of choice to characterise the evolution of its microstructure. UO2 crystallises in a fluorite CaF2 (space group Fm‐3m) structure that gives rise to a unique Raman signature, the T2g band. However, several other bands are often detected whose attribution remains unclear. The present study gives new insights on the Raman spectrum of UO2 thanks to the combination of isotopic labelling with 18O and Raman imaging. In addition to the expected T2g, U2 (LO), 2LO and U3 bands, we have detected a doublet at 885 and 925 cm−1, a U* band at 555 cm−1 in some specific areas and two bands located at 367 and 1196 cm−1. All Raman bands shift under the effect of the replacement of 16O by 18O, excepting for the U* band that could not be detected anymore. The isotopic shift ratio could be determined for 20% and 30% 18O labelling. No discrepancy in band position is observed between grains and grain boundaries, except for the U2(LO) band. We also evidence a difference between the U defect bands and the 885 and 925 cm−1 doublet bands evolution under labelling, although the latter also seems to be connected to the presence of defects in the material.

Size effects and the deformation behaviour of a dilute Mg-Zn-Ca alloy subjected to cyclic four-point bending

In biodegradable stents made from dilute Mg-Zn-Ca alloys a small number of grains constitute the thickness of a sample limiting the mechanical constrain typically seen in polycrystalline alloys. At the same time such stents are exposed to complex loading conditions, which could potentially lead to premature failure particularly in the presence of limited slip mode activation. In order to improve our understanding of the prevailing micromechanics for such conditions hot-rolled, thin strip samples were produced with thickness to grain size ratios (t/D) of 100 and 17. Samples were extracted from such thin strips and subjected to interrupted cyclic four-point bending in order to study the in-grain misorientation axis (IGMA) evolution of selected grains during cyclic loading using quasi-in-situ electron back-scattered diffraction (EBSD). Grains were selected at the tensile and compressive faces of samples, and in the vicinity of the neutral band. Analysis of the evolution of IGMA and misorientation profiles during the bending showed that extension twinning was the dominant deformation mode in the compressive region for both t/D ratios. In addition, non-basal <a>-type slip systems were active as a result of work hardening. In the tensile region, the activity of <a>-type non-basal slip systems was observed for the t/D of 100, but basal/double basal slip was the dominant deformation mode for the t/D of 17. No signs of failure were observed for the sample with a t/D of 17 at the tensile region, implying that these basal slip modes can accommodate deformation largely without the assistance of other deformation modes. The neutral band evolution was mapped using grain orientation spread (GOS) analysis. In contrast to the continuum mechanics solution, a neutral band was observed instead of an axis. The position of the neutral band was dependant on the local orientation organization of the grains and the extent of work-hardening.

Artificial Surface Electron Network Prompted Energy Band Structure Tuning: Boosting Solar-to-Hydrogen Evolution Performance.

The energy gap and conduction band position of catalysts play crucial roles in solar-to-hydrogen (STH) transformation technology. Unfortunately, although an increase in the conduction band position can effectively promote the photoreduction capacity of the photocatalyst, it will inevitably widen the band gap, thus reducing the light-absorption scale. It seems that there is a contradiction between the reduction of band gap and the improvement of conduction band position, which is that "You can't have your cake and eat it too." Herein, an ultrasimple molecular adsorption strategy was engineered by adsorbing hydrazine hydrate on the surface of TiO2. The theoretical and experimental results indicated that the strong electron-donating effect of amino groups in hydrazine hydrate can promote the redistribution of photogenerated electrons and form surface electron networks on the surface of TiO2 photocatalysts, which can bend the conduction band upward and significantly improve its photoreduction ability. Besides, the adsorption of -NH2 can narrow the band gap width of TiO2 and promote the separation efficiency of photogenerated carriers. More interestingly, it can also effectively enhance the adsorption of H2O and H+, thus greatly elevating the STH efficiency. The STH rate of the as-prepared T-N-3 can be increased by ≈530%. This work sheds light on a new approach for resolving the contradiction between photoreduction and light absorption capabilities to effectively enhance photocatalytic performance.

Structure evolution and energy band modulation in Ba-doped BiFeO3 thin films

Bi1−xBaxFeO3 (BBFO, x = 0, 0.03, 0.1) thin films were epitaxially grown on SrRuO3-buffered SrTiO3 (001) substrates by pulsed laser deposition. With increasing Ba content, the BBFO thin films show significantly reduced leakage currents but suppressed ferroelectric polarization. X-ray diffraction reciprocal space mappings and Raman spectra indicate a structural evolution from a rhombohedral-like to tetragonal-like phase in the BBFO thin films. Optical absorption and photoelectron spectroscopy measurements demonstrate a modulation of energy band structures in the BBFO thin films. With A-site Ba acceptor doping, the BBFO thin films exhibit a blue-shift of optical bandgap and an increase in work function. The energy positions of conduction and valence bands of the BBFO thin films have been modulated, and the Fermi level shifts down to the center of the forbidden band, but acceptor-doped BFO thin films still show n-type conduction. The presence of extra oxygen vacancies by acceptor doping is supposed to make contribution to conduction behavior. This study provides a method to manipulate the functional properties and gives insights into the physics of Ba doping in BFO thin films.

The Presence of Four Pathogenic Oral Bacterial Species in Six Wild Snake Species from Southern Taiwan: Associated Factors.

The oral cavity of snakes serves as a habitat for various microorganisms, some of which may include potential zoonotic pathogens posing risks to hosts and causing wound infections in snakebite victims. Clinical studies on snakebite cases in Taiwan have identified specific pathogens, such as Enterococcus faecalis (Gram-positive), Morganella morganii, Aeromonas hydrophila, and Pseudomonas aeruginosa (Gram-negative). However, the prevalence of these bacteria in the oral cavity of wild snakes remains largely unknown. This study investigated the occurrence of these bacteria in six wild snake species (Naja atra, Bungarus multicinctus, Trimeresurus stejnegeri, Protobothrops mucrosquamatus, Boiga kraepelini, and Elaphe taeniura friesi) from southern Taiwan, along with factors influencing their presence. Oropharyngeal swab samples were collected from a substantial number of wild-caught snakes (n = 1104), followed by DNA extraction, polymerase chain reaction, and gel electrophoresis. The band positions of samples were compared with positive and negative controls to determine the presence of target bacteria in each sample. The overall occurrence rates were 67.4% for E. faecalis, 31.5% for M. morganii, 8.2% for A. hydrophila, and 7.7% for P. aeruginosa. Among snake species, B. kraepelini exhibited dominance in E. faecalis (93.4%), A. hydrophila (17.1%), and P. aeruginosa (14.5%), while male N. atra showed dominance in M. morganii (51.3%). The occurrence of E. faecalis was lowest in winter. The results of multiple logistic regression analyses suggest that factors such as species, sex, temperature, season, and coexisting pathogens may have a significant impact on the occurrence of target bacteria. These findings have implications for wildlife medicine and snakebite management.

VCD spectra of chiral naphthalene-1-carboxamides in the solid-state

The VCD spectra of chiral 2,3-dihydro-1H-benzo[de]isoquinolin-1-one (8-substituted naphthalene-1-carboxamide, BIQ) were studied in KBr pellets. The X-ray diffractometry revealed that the Me, Ph, and pClPh BIQs crystalize in the monoclinic P21, while nBu, pMePh, and oMeOPh BIQs in the orthorhombic P212121 space group. Only the Me-BIQ crystal exhibits the presence of cyclic amide dimers, while the others contain chains of the amid group hydrogen bonds. For all BIQs, except pMePh, the most intense IR band in the 1750–1550 cm−1 region is located at ca. 1680 cm−1 and is accompanied by two weak ones at ca. 1618 and 1590 cm−1. For the pMePh derivative, four almost equally intense IR bands at 1662, 1639, 1614, and 1588 cm−1 are observed. This region of the IR spectra of BIQs, but pMePh, is well reproduced by calculations based on BIQ monomers. On the other hand, the complex IR pattern of pMePh is computationally reproduced when larger crystal fragments, like octamers, are considered. Registration of the VCD spectra enabled recognizing the complexity of IR contours at ca. 1680 cm−1 by the corresponding VCD motives. For (i) Me, Ph and pClPh (R)-enantiomers, two (+)(–) bands were distinguished and for (ii) nBu and pMePh ones, one VCD band with right-side asymmetry was found. For (iii) oMeOPh the VCD pattern cannot be unambiguously assigned. Thus, the VCD spectra in the ν(C=O) range diverse the studied compounds. Among the set of molecules, pMePh has exceptional crystal geometry. Therefore, its most intense ν(C=O) band position and shape can be connected with the geometry of the hydrogen bonds, interactions, and crystal packing. Interpretation of the VCD spectra is based on linear and packed BIQ octamers. This cluster model can reproduce the main features of the solid-state VCD of BIQs.

Morphology-Controlled ZnO@ZnWO4 Hetero-Nanostructures for Efficient Photooxidation of Water in Near-Neutral pH.

One-dimensional ZnO nanorods (NRs) have been extensively studied as photoanodes because of their unique optical properties, high electron mobility, and suitable band positions for water oxidation. However, their practical efficiency is often compromised by chemical instability during water oxidation and high carrier recombination rates. To overcome this issue, precise morphological control of ZnO@ZnWO4 core-shell structured photoanodes, featuring a ZnO core and a ZnWO4 shell was used. This was accomplished by depositing WO3 onto hydrothermally grown ZnO NRs using the thermal chemical vapor deposition process. The photoelectrochemical performance of ZnO@ZnWO4 with an optimized morphology outperforms that of pristine ZnO NRs. Systematic optical and electrochemical analyses of ZnO@ZnWO4 demonstrated that the enhancement is attributed to the enhanced charge transfer efficiency facilitated by the optimized ZnWO4 shells.

Comparative Study on Handheld, Modular, and Laboratory Raman Instruments for the Analysis of Colon Tissues and Colorectal Polyps

Portable Raman spectrometers may offer advantages for clinical medical diagnostics over laboratory instruments by allowing for quick measurements in the field and provision of data suitable for screening analyses. This work evaluates the potential of using available handheld, modular, and laboratory Raman spectrometers for screening normal colon tissues and benign and malignant colon polyps. The Raman spectra of tissue samples and reference biological macromolecules were measured with these instruments and analyzed using curve fitting and multivariate statistics. The spectra of calf thymus DNA measured with portable devices showed suitable signal-to-noise levels and half-widths of the prominent bands. Band positions, resolution, and relative intensities in the Raman spectra of colon tissues and reference compounds varied for the instruments, and the laboratory device demonstrated the best spectral feature. The principal component analysis (PCA) of the spectra obtained with all Raman devices showed well discrimination of normal colon tissue, adenomatous polyp, and adenocarcinoma. Dendrograms of similarity obtained using hierarchy cluster analysis (HCA) for the Raman spectra of all three devices also showed good separation of these samples. The soft independent modeling of class analogy (SIMCA) and support vector machine (SVM) models efficiently classified normal colon tissues and benign/malignant colorectal polyps based on the Raman data from all three devices. Despite its less pronounced spectral characteristics, the handheld Raman spectrometer can be used in early diagnosis of colorectal carcinoma, comparable to the modular and laboratory instruments.

Copper-decorated strategy based on defect-rich NH2-MIL-125(Ti) boosts efficient photocatalytic degradation of methyl mercaptan under sunlight

Photocatalysis has received significant attention as a technology that can solve environmental problems. Metal-organic frameworks are currently being used as novel photocatalysts but are still limited by the rapid recombination of photogenerated carriers, low photogenerated electron migration efficiency and poor solar light utilization rate. In this work, a novel photocatalyst was successfully constructed by introducing Cu species into thermal activated mixed-ligand NH2-MIL-125 (Ti) via defect engineering strategy. The constructed defect structure not only provided 3D-interconnected gas transfer channels, but also offered suitable space to accommodate introduced Cu species. For the most effective photocatalyst 0.2Cu/80%NH2-MIL-125 (300 °C) with optimized Cu content, the photocatalytic degradation rate of CH3SH achieved 4.65 times higher than that of pristine NH2-MIL-125 under visible light (λ > 420 nm). At the same time, it showed great degradation efficiency under natural sunlight, 100 ppm CH3SH was completely removed within 25 min in full solar light illumination. The improved catalytic efficiency is mainly due to the synergistic effect of the integrated Schottky junction and rich-defective NH2-MIL-125, which improved the bandgap and band position, and thus facilitated the separation and transfer of the photo-generated carriers. This work provided a facile way to integrate Schottky junctions and rich-defective MOFs with high stability. Due to its excellent degradation performance under sunlight, it also offered a prospective strategy for rational design of high-efficiency catalysts applied in environmental technologies.

Design of FeWO4@N-TiO2 nanocomposite and its enhanced photocatalytic activity in decomposing methylene blue and phenol under visible light

Effluents from textile industries contain high levels of methylene blue (MB) and phenol from other industries, which are serious health hazard and a threat to biodiversity as well as the environment. Nitrogen (N) doped TiO2 modified by iron tungstate (FeWO4) composite photocatalyst (FeWO4 @N-TiO2) working under visible light (λ ≥ 420 nm) could be a suitable candidate to degrade this pollutant. X-ray diffractometry (XRD) and X-ray Photoelectron Spectroscopy (XPS) study suggested that the N was introduced as substitutional doping into TiO2 lattice which leads to narrowing band gap of TiO2 nanoparticles. The prepared FeWO4 @N-TiO2 was utilized to measure efficiency in decomposing the methylene blue (MB) and phenol in aqueous phase under visible light (λ ≥ 420 nm) irradiation. The FeWO4 @N-TiO2 showed better catalytic efficiency to degrade MB and phenol in several compositions of FeWO4. The composite demonstrated 77% and 85% removal of MB and phenol from aqueous medium after 2 h of visible light illumination, respectively. Interestingly, radical-hole hunting identifying tests indicated the presence of hydroxyl radical (°OH) in the photocatalytic decomposition reaction medium. The higher efficiency of FeWO4 @N-TiO2 was originated from absorption of visible energy as well as the relative energy band positions of the components FeWO4 and N-TiO2. Thus, photoexcited electron (e‾) and hole (h+) could take part by inter-particle transfer through the formation of °OH radical which was experimentally confirmed and a photocatalytic reaction mechanism has been proposed to mineralize organics.

Tetrazine-Linked Covalent Organic Frameworks With Acid Sensing and Photocatalytic Activity.

The first synthesis and comprehensive characterization of two vinyl tetrazine-linked covalent organic frameworks (COF), TA-COF-1 and TA-COF-2, are reported. These materials exhibit high crystallinity and high specific surface areas of 1323 and 1114 m2 g-1. The COFs demonstrate favorable band positions and narrow band gaps suitable for light-driven applications. These advantages enable TA-COFs to act as reusable metal-free photocatalysts in the arylboronic acids oxidation and light-induced coupling of benzylamines. In addition, these TA-COFs show acid sensing capabilities, exhibiting visible and reversible color changes upon exposure to HClsolution, HCl vapor, and NH3 vapor. Further, the TA-COFs outperform a wide range of previously reported COF photocathodes. The tetrazine linker in the COF skeleton represents a significant advancement in the field of COF synthesis, enhancing the separation efficiency of charge carriers during the photoreaction and contributing to their photocathodic properties. TA-COFs can also degrade 5-nitro-1,2,4-triazol-3-one (NTO), an insensitive explosive present in industrial wastewater, in 20 min in a sunlight-driven photocatalytic process; thus, revealing dual functionality of the protonated TA-COFs as both photodegradation and Brønsted acid catalysts. This pioneering work opens new avenues for harnessing the potential of the tetrazine linker in COF-based materials, facilitating advances in catalysis, sensing, and other related fields.

Variations in surface adsorbed H2O on lunar soils and relevant minerals

Spectral variations due to the removal of surface adsorbed H2O at 3 and 6 μm in reflectance spectra on lunar soils and relevant minerals (olivine, pyroxene, and plagioclase) have been assessed. This study characterizes variations in hydration features as a function of lunar relevant surface temperatures, to further understand current (i.e., M3, HRI-IR, VIMS) and future (i.e., Lunar Trailblazer) observations of diurnal changes in surface hydration. Additionally, we explore the utility of using the 6 μm H2O feature to discern the speciation of surface hydration at 3 μm. We perform controlled temperature measurements (25–200 °C) in a Linkam THMS600 Environmental Stage fixed to a Bruker LUMOS Microscope Fourier Transform IR (μFTIR) spectrometer. We observe clear and systematic changes in the strength of the 3 μm H2O/OH feature associated with the thermal removal of adsorbed H2O, in addition to changes in the overall shape and band position of the feature in both the terrestrial and lunar samples. The strength of the 3 μm feature for the compositionally distinct and relatively brighter Apollo highland soil (62231) is stronger and more symmetric than the 3 μm feature observed for the darker mare soil (10084). While several silicate related absorption features are identified near 6 μm, neither a distinguishable hydration feature nor any changes in reflectance that could be attributed to the presence or a change in the amount of surface adsorbed H2O were observed at 6 μm.

Mechanism of p-Type Heteroatom Doping of Lithium Stannate for the Photodegradation of 2,4-Dichlorophenol: Enhanced Hole Oxidative Capability and Concentrations.

A systematic evaluation of enhancing photocatalysis via aliovalent cation doping is conducted. Cation In3+, being p-type-doped, was chosen to substitute the Sn site (Sn4+) in Li2SnO3, and the photodegradation of 2,4-dichlorophenol was applied as a model reaction. Specifically, Li2Sn0.90In0.10O3 exhibited superior catalytic performance; the photodegradation efficiency reached about 100% within only 12 min. This efficiency is far greater than that of pure Li2SnO3 under identical conditions. Density functional theory calculations reveal that introducing In3+ increased the electron mobility, yet decreased the hole mobility, leading to photogenerated carrier separation. However, photoluminescence and time-resolved photoluminescence suggest that In3+ induced nonradiative coupling in the matrix, reducing the photogenerated carrier separation ratio compared with that of Li2SnO3. The optical band gap of Li2Sn0.90In0.10O3 was almost unchanged compared with that of Li2SnO3 via ultraviolet-visible absorption. The increased photocatalytic efficiency was ascribed to the lower valence band position and enhanced hole concentrations by valence band X-ray photoelectron spectroscopy and electrochemical measurements. Finally, a 2,4-dichlorophenol degradation pathway, an intermediate toxicity assessment, and a photocatalytic mechanism were proposed. This work offers insights into designing and optimizing semiconductor photocatalysts with high performance.

Spectroscopic investigation of size-dependent CO2 binding on cationic copper clusters: analysis of the CO2 asymmetric stretch.

Photofragmentation spectroscopy, combined with quantum chemical computations, was employed to investigate the position of the asymmetric CO2 stretch in cold, He-tagged Cun[CO2]+ (n = 1-10) and Cun[CO2][H2O]+ (n = 1-7) complexes. A blue shift in the band position was observed compared to the free CO2 molecule for Cun[CO2]+ complexes. Furthermore, this shift was found to exhibit a notable dependence on cluster size, progressively redshifting with increasing cluster size. The computations revealed that the CO2 binding energy is the highest for Cu+ and continuously decreases with increasing cluster size. This dependency could be explained by highlighting the role of polarization in electronic structure, according to energy decomposition analysis. The introduction of water to this complex amplified the redshift of the asymmetric stretch, showing a similar dependency on the cluster size as observed for Cun[CO2]+ complexes.

Leak-out spectroscopy as alternative method to rare-gas tagging for the Renner-Teller perturbed HCCH+ and DCCD+ ions.

Infrared messenger-tagging predissociation action spectroscopy (IRPD) is a well-established technique to record vibrational spectra of reactive molecular ions. One of its major drawbacks is that the spectrum of the messenger-ion complex is taken instead of that of the bare ion. In particular for small open-shell species, such as the Renner-Teller (RT) affected HCCH+ and DCCD+, the attachment of the tag may have a significant impact on the spectral features. Here we present the application of the novel leak-out spectroscopy (LOS) as a tag-free method to record the cis-bending of the HCCH+ (∼700 cm-1) and DCCD+ cations (∼520 cm-1), using a cryogenic ion trap end user station at the FELIX laboratory. We demonstrate that the obtained LOS spectrum is equivalent to a previously recorded laser-induced reactions (LIR) spectrum of HCCH+. The bending modes are the energetically lowest-lying vibrational modes targeted with LOS so far, showing its potential as a universal broadband spectroscopic technique. Furthermore, we have investigated the effect of the rare gas attachment by recording the vibrational spectra of Ne- and Ar-tagged HCCH+. We found that the Ne-attachment led to a shift in band positions and change in relative intensities, while the Ar-attachment even led to a complete quenching of the RT splitting, showing the importance of using a tag-free method for RT affected systems. The results are interpreted with the help of high-level ab initio calculations in combination with an effective Hamiltonian approach.

Near-infrared absorption and radiative cooling of naphthalene dimers (C10H8)2.

The radiative cooling of naphthalene dimer cations, (C10H8)2+ was studied experimentally through action spectroscopy using two different electrostatic ion-beam storage rings, DESIREE in Stockholm and Mini-Ring in Lyon. The spectral characteristics of the charge resonance (CR) band were observed to vary significantly with a storage time of up to 30 seconds in DESIREE. In particular, the position of the CR band shifts to the blue, with specific times (inverse of rates) of 0.64 s and 8.0 s in the 0-5 s and 5-30 s storage time ranges, respectively. These long-time scales indicate that the internal energy distribution of the stored ions evolves by vibrational radiative cooling, which is consistent with the absence of fast radiative cooling via recurrent fluorescence for (C10H8)2+. Density functional based tight binding calculations with local excitations and configuration interactions (DFTB-EXCI) were used to simulate the absorption spectrum for ion temperatures between 10 and 500 K. The evolution of the bandwidth and position with temperature is in qualitative agreement with the experimental findings. Furthermore, these calculations yielded linear temperature dependencies for both the shift and the broadening. Combining the relationship between the CR band position and the ion temperature with the results of the statistical model, we demonstrate that the observed blue shift can be used to determine the radiative cooling rate of (C10H8)2+.

Exploring flat-band properties in two-dimensional M3QX7 compounds.

We present a computational study of the M3QX7 family of two-dimensional compounds, focusing specifically on their flat-band properties. We use a high-throughput search methodology, accelerated by machine learning, to explore the vast chemical space spawned by this family. In this way, we identify numerous stable 2D compounds within the M3QX7 family. We investigate how the chemical composition can be manipulated to modulate the position and dispersion of the flat bands. By employing a tight-binding model we explain the formation of flat bands as a result of a relatively loose connection between triangular M3QX3 clusters via bridges of X atoms. The model provides an understanding of the residual interactions that can impact the band dispersion. The same loose connection between clusters not only leads to strongly localized electronic states and thus flat electronic bands but also leads to localized phonon modes and flat bands in the phonon dispersion.