Fundamental Band Research Articles

Vibrational Mode-Dependent Circular Dichroism of Jet-Cooled Styrene Oxide.

Vibrational mode-dependent circular dichroism (CD) effects in vibrational CD spectra are often used to determine the handedness of molecules with multiple chiral centers. Here, we investigate vibrational mode-dependent CD effects in the electronic CD spectra of jet-cooled (R)-(+)- and (S)-(-)-styrene oxide obtained by using resonant two-photon ionization CD (R2PICD) spectroscopy. Although most fundamental vibronic bands demonstrated CD signatures consistent with that of the origin band, the overtone and combination bands exhibited opposite CD signatures. Theoretical calculations suggest that CD in fundamental bands are primarily governed by Franck-Condon contributions, whereas Herzberg-Teller contributions, which reflect the influences of vibrational modes on CD values, become more significant in overtone and combination bands. These results underscore the potential of mode-dependent vibronic CD signals in R2PICD spectra for determining the absolute configurations of molecules with multiple chiral centers.

Interband cascade laser absorption sensor for sensitive measurement of hydrogen chloride in smoke-laden gases using wavelength modulation spectroscopy

A tunable interband cascade laser sensor, based on wavelength modulation absorption spectroscopy near 3.73 µm, was developed to measure hydrogen chloride gas concentration in smoke-laden environments associated with the overhaul stages of firefighting. Wavelength selection near 2678cm−1 targets the P(0,9) transition within the fundamental vibrational band of HCl, chosen for its absorption strength and isolation from CO2, H2O, and CH4, as well as proximity to absorption features of other toxicant gases of interest in firefighting applications. Both scanned-wavelength direct absorption with a Voigt lineshape-fitting routine and a wavelength modulation spectroscopy absorption method are employed to recover species concentration. The laser sensor is paired with a compact commercial off-the-shelf 1 m multipass optical gas cell modified to use polished Alloy 20 steel mirrors for increased corrosion resistance against humid and acidic gases, and it is tested by sampling effluent gases from pyrolyzing and burning solid samples of polyvinyl chloride under a radiant heating apparatus in a laboratory fume hood. The wavelength modulation spectroscopy method is demonstrated to enable measurement at the near-ppm-level within a compact form-factor and to provide insights into the thermochemical pyrolysis processes that lead to the formation of hydrogen chloride when polyvinyl chloride is exposed to radiant heating.

JWST/NIRSpec Observations of Brown Dwarfs in the Orion Nebula Cluster

We have used the multiobject mode of the Near-Infrared Spectrograph (NIRSpec) on board the James Webb Space Telescope (JWST) to obtain low-resolution 1–5 μm spectra of 22 brown dwarf candidates in the Orion Nebula Cluster, which were selected with archival images from the Hubble Space Telescope. One of the targets was previously classified as a Herbig–Haro (HH) object and exhibits strong emission in H i, H2, and the fundamental band of CO, further demonstrating that HH objects can have bright emission in that CO band. The remaining targets have late spectral types (M6.5 to early L) and are young based on gravity-sensitive features, as expected for low-mass members of the cluster. According to theoretical evolutionary models, these objects should have masses that range from the hydrogen burning limit to 0.003–0.007 M ⊙. Two of the NIRSpec targets were identified as proplyds in earlier analysis of Hubble images. They have spectral types of M6.5 and M7.5, making them two of the coolest and least massive known proplyds. Another brown dwarf shows absorption bands at 3–5 μm from ices containing H2O, CO2, OCN−, and CO, indicating that it is either an edge-on class II system or a class I protostar. It is the coolest and least massive object that has detections of these ice features. In addition, it appears to be the first candidate for a protostellar brown dwarf that has spectroscopy confirming its late spectral type.

Experimental Polarizability Transition Moments of CO2 for Excited Vibrational States.

The Raman spectrum of CO2 from room temperature to 1800 K has been measured in a series of experiments. The differential Raman scattering cross-sections for the fundamental bands at 1285.41 cm-1 and 1388.18 cm-1 have been obtained from reference bands of H2 and N2 as intensity standards. The Raman cross-sections of CO2 hot bands, involving vibrational energy levels up to 5000 cm-1, were derived from those of the fundamental bands. The Raman cross-sections obtained this way were reduced to transition moments of the mean molecular polarizability, which make it possible to simulate the Raman spectrum of CO2 up to 2000 K. This paves the way for local or remote diagnostics of CO2 in hot environments using Raman based techniques.

Comprehensive evaluation of mechanical properties, optoelectronic features, photovoltaic performance, and crystal stability of Ba3MX3 (M = As, Sb; X = Cl, Br, I)

Herein, the first-principles computations are utilized to study the optoelectronic properties, photovoltaic performance, crystal stability, and mechanical features of Ba3MX3 (M = As, Sb; X = Cl, Br, I). Through comprehensive structural stability evaluation, all compounds are determined to be stable. The results indicate that Ba3MX3 (M = As, Sb; X = Cl, Br) is brittle while both Ba3AsI3 and Ba3SbI3 are ductile. The HSE06-based electronic structure calculations show that the direct-gap nature is revealed for six compounds, and the energy band gaps are within the range of 1.35–1.65 eV. The fundamental band gap can be modulated by virtue of X-anion substitution. The low carrier effective masses are disclosed for these compounds. Their optical features exhibit that high solar absorption and weak reflectance and energy loss are observed. Ultimately, an ultra-high theoretical conversion efficiency of 31.9 % is implemented for Ba3MI3 (M = As, Sb). Besides, the remaining four compounds also have high conversion efficiencies within 29–30 %. From the suitability for practical applications, both Ba3AsI3 and Ba3SbI3 are chosen as the best candidates for the absorber layers of effective single-junction solar cells. Our findings unveil the suitability of these inorganic materials for optoelectronic applications.

Impact of gamma irradiation on optical and nonlinear properties of Indium chloride phthalocyanine thin films

This study investigates the impact of gamma radiation on indium chloride phthalocyanine (lnPcCl) thin films, which were prepared via vacuum thermal evaporation. x-ray diffraction revealed the amorphous structure of the films, with increasing gamma doses causing more noticeable structural disorders. Optical analysis showed a slight decrease in the optical band gap energy and a significant reduction in the fundamental band gap energy. Additionally, higher gamma doses led to decreased transmittance and increased reflectance. The study also observed substantial enhancements in nonlinear optical parameters, such as third-order nonlinear susceptibility (χ(3)) and nonlinear refractive index (n 2). These findings suggest the potential of gamma-irradiated lnPcCl films for advanced optoelectronic and nonlinear optical applications.

Ultrasound Imaging of Nonlinear Media Response Using a Pressure-Dependent Nonlinearity Index

It has been shown that within the range of acoustic pressures used in ultrasound imaging, waveforms are distorted during propagation in tissue due to the physically nonlinear behavior of the tissue. This distortion leads to changes in the spectrum of the received ultrasound echoes, causing the transfer of signal energy from the fundamental frequency to higher harmonics. Interestingly, adipose tissue exhibits up to 50 % stronger nonlinear behavior compared to other soft tissues. The tissue nonlinearity parameter B/A is typically measured ex vivo using an ultrasound method in transmission mode, which requires extensive receiving systems. Currently, there is no improved ultrasound method for measuring the B/A nonlinearity parameter in vivo, which could be used in assessing the degree of fatty liver disease. We propose a new, simple approach to estimating nonlinear tissue properties. The proposed method involves transmitting ultrasound waves at significantly different acoustic pressures, recording echoes only in the fundamental frequency band at various depths, and introducing a nonlinearity index (NLI) based on specific echo amplitude ratios. The NLI at a given depth is calculated using the ratio of two dimensionless parameters. The first parameter is a predetermined constant obtained by dividing the total echo values from transmitting a signal at higher sound pressure by those from a signal at lower sound pressure, summed over a small tissue sample volume located near the transducer. The second parameter is calculated at a fixed distance from the transducer, determined by dividing the total echo values from transmitting a signal at higher sound pressure by those from a signal at lower pressure, summed over a small tissue volume of the tissue at that distance from the transducer. The reliability of the proposed measurements for assessing tissue nonlinearity has been substantiated through experimental confirmation of the existing correlations between the values of NLI and B/A in water, sunflower oil, and animal liver tissue samples with oil-enriched regions. The NLI was more than 15 % higher in sunflower oil than in water. The NLI in bovine liver sample below the area with injected oil (mimicking “steatosis”) was more than 35 % higher than in regions without oil. This method represents a promising modality for the nonlinear characterization of tissue regions in vivo, particularly for diagnosing fatty liver disease.

First-Principles Calculations of the Structural, Mechanical, Optical, and Electronic Properties of X2Bi4Ti5O18 (X = Pb, Ba, Ca, and Sr) Bismuth-Layered Materials for Photovoltaic Applications

For the first time, density functional theory (DFT) calculations have been employed for the measurement of the structural, mechanical, optical, and electrical properties of a bismuth-layered structure ferroelectrics (BLSFs) family member possessing an orthorhombic structure with Cmc21 space group. Based on the exchange–correlation approximation, our calculations show that Pb2Bi4Ti5O18 possesses an indirect band gap, while the materials X2Bi4Ti5O18 (X = Ba, Ca, and Sr) demonstrate direct band gap, where the estimated density functional fundamental band gap values lie between 1.84 to 2.33 eV, which are ideal for photovoltaic applications. The optical performance of these materials has been investigated by tuning the band gaps. The materials demonstrated outstanding optical characteristics, such as high absorption coefficients and low reflection. They exhibited impressive absorption coefficient (α = 105 cm−1) throughout a broad energy range, especially in the visible spectrum (105 cm−1 region). The findings show that the compounds demonstrate lower reflectivity in the visible and UV regions, making them suitable for single-junction photovoltaic cells and optoelectronic applications. The Voigt–Reuss–Hill averaging technique has been employed to derive elastic parameters like bulk modulus (B), Young’s modulus, shear modulus (G), the Pugh ratio (B/G) and the Frantesvich ratio (G/B) at 0.1 GPa. The mechanical stability of the compounds was analyzed using the Born stability criteria. Pugh’s ratio and Frantesvich’s ratio show that all the compounds are ductile, making them ideal for flexible optical applications.

CORINOS. II. JWST-MIRI Detection of Warm Molecular Gas from an Embedded, Disk-bearing Protostar

We present James Webb Space Telescope (JWST) Mid-InfraRed Instrument (MIRI) observations of warm CO and H2O gas in emission toward the low-mass protostar IRAS 15398-3359, observed as part of the CORINOS program. The CO is detected via the rovibrational fundamental band and hot band near 5 μm, whereas the H2O is detected in the rovibrational bending mode at 6–8 μm. Rotational analysis indicates that the CO originates in a hot reservoir with an excitation temperature of 1598 ± 118 K, while the water is much cooler at 204 ± 7 K. Neither the CO nor the H2O line images are significantly spatially extended, constraining the emission to within ∼40 au of the protostar. The compactness and high temperature of the CO are consistent with an origin in the embedded protostellar disk, or in a compact disk wind. In contrast, the water must arise from a cooler region and requires a larger emitting area (compared to the CO) to produce the observed fluxes. The water may arise from a more extended part of the disk, or from the inner portion of the outflow cavity. Thus, the origin of the molecular emission observed with JWST remains ambiguous. Better constraints on the overall extinction, comparison with realistic disk models, and future kinematically resolved observations may all help to pinpoint the true emitting reservoirs.

Compact vertical emitting ring interband cascade lasers for isotope-resolved CO2 sensing

We present a compact vertically emitting ring interband cascade laser (ICL) with low power consumption and the possibility for seamless integration into various CO2 sensing applications. Our devices exhibit desirable performance characteristics in battery-driven handheld devices, including room temperature (20 °C) threshold currents as low as 15 mA, small footprints, and stable single-mode emission, suitable for rapid isotope-resolved CO2 detection. Through epi-down bonding with sub-micron accuracy, we achieved robust integration of substrate-emitting ring ICLs, ensuring reliability and scalability that would be required for mass production. We present comprehensive experimental results validating the efficacy of our approach, including spectral analysis and CO2 sensing capabilities with limits of detection of 24 and 13 ppmv utilizing the 12CO2 P(60) and 13CO2 R(10) transitions in the ν3 fundamental band, respectively. The demonstrated devices hold great promise for a wide range of industrial applications, including environmental monitoring, process control, and atmospheric research, where compact low-power sensors are essential.

New experimental measurements of the Collision Induced Absorptions of H2-H2 and H2-He in the 3600-5500 cm−1 spectral range from 120 to 500 K

The Collision-Induced Absorption (CIA) fundamental band of H2 has been studied in the 3600-5500 cm−1 spectral range for temperatures ranging from 120 to 500 K for both a pure H2 gas and a H2-He mixture. We used a simulation chamber called PASSxS (Planetary Atmosphere System Simulation x Spectroscopy) developed at INAF/ISAC which contains a Multi-Pass cell interfaced with a Fourier Spectrometer, aligned to reach an optical path of 3.28 m. The H2-H2 and H2-He binary absorption coefficients (BACs) have been derived for seven temperatures in the chosen range and provided in tabular form, including the unexplored high-temperature range above 300 K. We also calculated the integral of the H2-H2 and H2-He experimental BACs in the reduced 4000-5000 cm−1 spectral range, finding a linear trend with temperature in both cases. The integrals have also been computed with larger uncertainties for the whole band, in the total 3600-5500 cm−1 spectral range including the band's wings, partially affected by the water vapor absorption. The integrals calculated over the whole and reduced spectral ranges are collected in tables. In addition, we performed measurements with a H2-He mix for different mixing ratios to explore possible deviations from the linear combination of the BACs. The experimental BACs have been shown in comparison with Abel and Borysow's ab initio models for a temperature of about 400 K, resulting in a good agreement over almost the whole spectral range, with a maximum deviation around the main peak of the band. Data and models also show a good agreement in the linear trend of the integrated BACs with temperature, apart from the H2-H2 Borysow's BACs, which follow a quadratic trend. Finally, we resolved all the interference dips, which were not taken into account by the existing theoretical models.

High-efficiency mid-infrared CW-seeded optical parametric generation in PPLN waveguide

Mid-infrared optical sources have been extensively used in a variety of applications, including gas sensing and metrology, by exploiting the fingerprint fundamental vibrational absorption bands of molecules in this spectral region. Parametric frequency conversion techniques, such as optical parametric generation (OPG) and optical parametric oscillator (OPO), represent common methodologies for mid-infrared generation. Notably, continuous-wave (CW)-seeded OPG exhibits superior stability and performance compared to conventional OPG. Here, we present a simple method for mid-infrared source generation based on femtosecond OPG in periodically poled lithium niobate (PPLN) waveguides. In addition to its robustness and simplicity, mid-infrared CW-seeded OPG features a high quantum conversion efficiency of 46.5% and a low threshold. The phase of CW-seeded OPG was passively referenced to the CW laser, making it suitable for dual-comb applications. This system shows great promise in the miniaturization of mid-infrared combs and will be applied to non-laboratory applications, including open-path atmospheric gas sensing and portable environmental monitoring.

Quantum computations on a new neural network potential for the proton-bound noble-gas Ar[formula omitted]H[formula omitted] complex: Isotopic effects

High-quality data-driven potentials were developed aiming to predict rovibrational traits and analyze the influence of the isotopic substitution on the molecular spectroscopic properties of Ar2H+. Neural networks machine-learning approaches trained on CCSD(T)/CBS datasets were implemented. Our full-dimensional quantum MCTDH results were discussed in comparison with experimental data in gas phase and solid matrix environments, as well as against theoretical estimates available. The new data indicate that both fundamental and progression bands are dominantly driven by the strength and shape of the underlying interactions. Our simulations could enable the spectroscopic characterization of these species, assisting investigations for their astrophysical observation.

First Ab Initio Line Lists for Triatomic Sulfur-Containing Molecules: S2O and S3.

We present in this paper the first room temperature rovibrational line lists for the main isotopologues of disulfur monoxide (S2O) and thiozone (S3) variationally computed from newly developed ab initio potential energy and dipole moment surfaces (PESs and DMSs). S2O and S3 are supposed to be potential candidates for astronomical detection, especially in the Venusian atmosphere where sulfur chemistry plays a major role. Contrary to other stable sulfur-containing species like SO2 or H2S, there is much less experimental data for the short-lived reactive S2O and S3 molecules. Indeed, the infrared spectra of S2O and S3 are quite complicated to analyze without consistent theoretical predictions because they contain both high J (∼100) and a lot of hot band transitions, even at T = 296 K. In this work, we have constructed PESs based on the single-reference coupled cluster approach [CCSD(T)] and including corrections due to the scalar relativistic effects, DBOC, and highly excited Slater determinants. The structure of the excited electronic states of S3 was also discussed. The nuclear-motion Eckart-Watson Hamiltonian expressed in terms of normal-mode irreducible tensor operators was used to compute the energy levels. For line intensity calculation, ab initio DMSs were computed at the CCSD(T)/aug-cc-pV5Z level of the theory. Rotation-vibration patterns in the fundamental bands of S2O and S3 have been simulated taking into account the recent Fourier-transform spectra of S2O recorded at the SOLEIL synchrotron. The present work aims at providing line intensities of S2O and S3 that are missing in the literature as well as new spectroscopic support for atmospheric applications.

H_3^+ absorption and emission in local (U)LIRGs with JWST NIRSpec: Evidence for high H_2 ionization rates

We study the $3.4-4.4$ fundamental rovibrational band of H$_3^+$, a key tracer of the ionization of the molecular interstellar medium (ISM), in a sample of 12 local ($d$$<$400\,Mpc) (ultra)luminous infrared galaxies ((U)LIRGs) observed with JWST NIRSpec. The P, Q, and R branches of the band are detected in 13 out of 20 analyzed regions within these (U)LIRGs, which increases the number of extragalactic H$_3^+$ detections by a factor of 6. For the first time in the ISM, the H$_3^+$ band is observed in emission; we detect this emission in three regions. In the remaining ten regions, the band is seen in absorption. The absorptions are produced toward the $3.4-4.4$ hot dust continuum rather than toward the stellar continuum, indicating that they likely originate in clouds associated with the dust continuum source. The H$_3^+$ band is undetected in Seyfert-like (U)LIRGs where the mildly obscured X-ray radiation from the active galactic nuclei might limit the abundance of this molecule. For the detections, the H$_3^+$ abundances, $N($H$_3^+$) H (0.5--5.5)times 10$^ imply relatively high ionization rates, $ H_2 $, of between 3times 10$^ $ and $>$4times 10$^ $, which is lower than the molecular outflow velocities measured using other tracers such as OH\,119 or rotational CO lines. This suggests that H$_3^+$ traces gas close to the outflow-launching sites before it has been fully accelerated. We used nonlocal thermodynamic equilibrium models to investigate the physical conditions of these clouds. In seven out of ten objects, the H$_3^+$ excitation is consistent with inelastic collisions with H$_2$ in warm translucent molecular clouds kin $sim 250--500\,K and H_2 )$sim 10$^ $). In three objects, dominant infrared pumping excitation is required to explain the absorptions from the (3,0) and (2,1) levels of H$_3^+$ detected for the first time in the ISM.

Composition Modulation-Mediated Band Alignment Engineering from Type I to Type III in 2D vdW Heterostructures.

Band alignment engineering is crucial for facilitating charge separation and transfer in optoelectronic devices, which ultimately dictates the behavior of Van der Waals heterostructures (vdWH)-based photodetectors and light emitting diode (LEDs). However, the impact of the band offset in vdWHs on important figures of merit in optoelectronic devices has not yet been systematically analyzed. Herein, the regulation of band alignment in WSe2/Bi2Te3- xSex vdWHs (0 ≤ x ≤ 3) is demonstrated through the implementation of chemical vapor deposition (CVD). A combination of experimental and theoretical results proved that the synthesized vdWHs can be gradually tuned from Type I (WSe2/Bi2Te3) to Type III (WSe2/Bi2Se3). As the band alignment changes from Type I to Type III, a remarkable responsivity of 58.12 AW-1 and detectivity of 2.91×1012 Jones (in Type I) decrease in the vdWHs-based photodetector, and the ultrafast photoresponse time is 3.2 µs (in Type III). Additionally, Type III vdWH-based LEDs exhibit the highest luminance and electroluminescence (EL) external quantum efficiencies (EQE) among p-n diodes based on Transition Metal Dichalcogenides (TMDs) at room temperature, which is attributed to band alignment-induced distinct interfacial charge injection. This work serves as a valuable reference for the application and expansion of fundamental band alignment principles in the design and fabrication of future optoelectronic devices.

Investigation of structural, optical, and magnetic properties of NiFe2O4 for efficient photocatalytic degradation of organic pollutants through photo fenton reactions

Nowadays, water pollution generated from textile effluents is one of the major problems for the human race and ecology. Hence, development of sustainable strategies to lower the water pollution level has become a burning need. In this regard, the present study focuses on the preparation of nano catalyst NiFe2O4 to catalyze the chemical reactions on industrial organic dyes for their fast cleansing from water. By sol-gel auto-combustion technique, NiFe2O4 nanoparticles were synthesized and exposed to thermal process at temperatures of 400, 600, and 800 °C. Highly crystalline phase with spinel cubic structured NiFe2O4 was formed with a crystal size of 18.71 nm, which was confirmed by XRD analysis. The FTIR spectra showed two fundamental absorption bands in the range 597.80–412.59 cm−1, which are the characteristics of tetrahedral M − O and octahedral M − O bond in NiFe2O4. The surface morphology of calcined NiFe2O4 was investigated by scanning electron microscope (SEM). The nanoparticle size analyzer exhibited that the synthesized NiFe2O4 nanoparticles had an average particle size of ∼ 291.3 nm. Three stage decomposition patterns were observed for NiFe2O4, which was analyzed by a temperature programmed STA. Zeta potential analyzer showed that the synthesized sample S1 and S2 were stable in the dispersion medium. Also, NiFe2O4 exhibited optical band gap energies for direct band transitions within the visible spectrum measured to be 1.43–1.45 eV, rendering them effective as photocatalysts under sunlight. The samples showed magnetic measurements by VSM with saturation magnetization, coercivity, remnant magnetization value of 66.81 emu/g, 4.13 Oe and 12.94 emu/g, respectively. The synthesized photocatalyst, NiFe2O4, at 400 °C, significantly degraded three toxic organic pollutants—Methylene blue, Rhodamine B, and Congo Red—under visible light through ‘Photo-Fenton’ reaction mechanisms. Among the three dyes, Methylene Blue exhibited the highest degradation percentage with a rate constant of 0.0149 min−1 and followed pseudo-first-order kinetic model.

Synchrotron radiation far infrared spectrum of the astrophysically significant Ethanol (CH3CH2OH) molecule in the gauche states in the vibrational ground state and other infrared observations

In this communication, the analyses of synchrotron radiation far infrared (FIR) spectrum corresponding to the gauche- (e1ando1) states of Ethyl Alcohol are reported. Detailed assignments have been performed for b-type transitions for K values ranging from 5 to 32 and up to a maximum J value of 50. The assignments confirmed the earlier microwave (MW) and millimeter wave (MMW) spectroscopic results. The transition wavenumbers have been used to determine the term values for the gauche-states involved for all the K and J values for which observation has been made. About 2000 spectral lines have been assigned, including some accurately calculated lines that fall in the MW and MMW regions. Although transitions between the trans-species and gauche species are not allowed in Ethanol, many resonances and level crossings of energy levels cause forbidden transitions. One such system of level crossings between K=10o1 and 12ee00 has been analyzed in detail, and the interaction coefficient determined. The state mixing seems quite strong and causes forbidden transitions (ΔK=0,2,3), including transitions for trans↔gauche, have been found. In addition, many new strong transitions have been assigned, which belong to the trans-species. To extend our work to higher wave numbers to facilitate observations made by the infrared detector on board the James Webb Space Telescope (JWST), the analysis of the torsional fundamental band transitions (around 220cm-1) for o2←e0 and o2←e1 has been taken up. Some of the assignments are discussed here. Lastly, the lower-lying vibrational bands centered around 425cm-1 (CCO– bending mode) and the band at around 800cm-1 (CH3- rocking mode) have been recorded. The CCO bending band shows an unmistakable parallel character for the trans-species. The assignment work on the CCO-bending band is in progress, and the assignments for K=0andK=1(+and-) are included in this report. Accurate term values for the CCO-bending mode could be obtained. The results allowed the determination of the leading rotational constants for the trans-species in the excited vibrational state of the CCO-bending state. The complete known assigned lines of about 16,000 lines for the parent isotopomer and about 650 lines for 13 -C1 and 13−C2 (see graphical abstract) substituted Ethanol isotopomers are gathered in Appendix I and II, respectively. These atlases should be a valuable tool for further energy level analysis and astronomical detection of Ethanol in interstellar space.

Continuum absorption in pure N[formula omitted] gas and in its mixture with Ar

The N2−N2and N2−Arcontinuum absorption spectra are calculated using the classical trajectory-based simulation (CTS). The spectra obtained are validated by new measurements in the subTHz spectral range along with the previously reported data in the far infrared. A novelty of our approach consists in the use of the CTS method to simulate both the fundamental nitrogen absorption band and the rototranslational band in N2−Ar, i.e., we succeeded to step beyond the conventionally used approximation of the only rigid monomers. This extension of the theory made it possible, in particular, to demonstrate the validity of the rigid monomer assumption for the CTS simulation of the rototranslational N2−Arband. The broadband spectra within 77–354 GHz were measured using the resonator spectrometer at temperatures of 278–333 K and pressures of 900–1600 Torr. A minor underestimation of the calculated absorption by 3.7% and 5% is shown for the N2−N2and N2−Arsystem, respectively. On the basis of the obtained data, a new analytical model is developed for the N2−N2absorption in the subTHz range, which can be used in radiation propagation codes for the Earth, Titan, or other nitrogen-rich atmospheres. The advantage of the model proposed here over those previously published is discussed.

Direct, Indirect, and Self-Trapped Excitons in Cs2AgBiBr6.

Cs2AgBiBr6 exhibits promising photovoltaic and light-emitting properties, making it a candidate for next-generation solar cells and LED technologies. Additionally, it serves as a model system within the family of halide double perovskites, offering insights into a broader class of materials. Here, we study various possible excited states of this material to understand its absorption and emission properties. We use time-dependent density functional theory (TD-DFT) coupled with nonempirical hybrid functionals, specifically PBE0(α) and dielectric-dependent hybrids (DDH) to explore direct, indirect, and self-trapped excitons in this material. Based on comparison with experiment, we show that these methods can give excellent predictions of the absorption spectrum and that the fundamental band gap has been underestimated in previous computational studies. We connect the experimental photoluminescence signals at 1.9-2.0 eV to the emission from self-trapped excitons and electron polarons. Finally, we reveal a complex landscape with energetically competing direct, indirect, and self-trapped excitons in the material.