Band Shape Research Articles

Polarimetric Radar Observations of Biological Scatterers in the Eye of Typhoon Lekima (2019)

AbstractTropical cyclones not only cause strong winds and heavy rainfall, but they can also facilitate the transport of birds and insects from tropical regions to areas along their paths. Before super Typhoon Lekima made landfall in 2019, an operational polarimetric radar in Wenzhou City observed biological scatterers in the typhoon's eye. These scatterers were likely birds and insects that were trapped in the calm center of the typhoon by strong winds and heavy rain. The polarimetric variables of these biological scatterers had specific characteristics: low reflectivity factor (ZH) values with a median of 7.5 dBZ, low cross‐correlation coefficient (ρhv) values with a median of 0.65, large differential reflectivity (ZDR) values with a median of 2.8 dB and a maximum of ∼7.8 dB, and widely‐distributed differential phase (ΦDP) values with 25th and 75th percentiles ranging from 1.8° to 36.0° and a median of 20.1°. When the edge of the eye reached the coastline, the birds and insects landed, with the biological scatterer signature changing from a circular shape to a band shape. We further compared Lekima with Atlantic Hurricane Irene which happened in 2011, and both storms had similar polarimetric characteristics contributed by both birds and insects. However, the biological echoes in Lekima better exhibited the characteristics of birds with a larger proportion of samples with ZDR lower than 5 dB as well as large ΦDP and low ρhv values. This finding could help to understand the role of typhoons in driving biological migration between oceans and/or islands and continents.

Theoretical spectroscopy for unraveling the intensity mechanism of the optical and photoluminescent spectra of chiral Re(I) transition metal complexes.

In this work, we present a computational study that is able to predict the optical absorption and photoluminescent properties of the chiral Re(I) family of complexes [fac-ReX(CO)3L], where X is either Cl or I and L is N-heterocyclic carbene extended with π-conjugated [5]-helicenic unit. The computational strategy is based on carefully calibrated time dependent density functional theory calculations and operates in conjunction with an excited state dynamics approach to treat in addition to absorption (ABS) and photoluminescence (PL), electronic circular dichroism (ECD), and circularly polarized luminescence (CPL) spectroscopies, respectively. The employed computational approach provides, an addition, access to the computation of phosphorescence rates in terms of radiative and non-radiative relaxation processes. The chosen molecules consist of representative examples of non-helicenic (NHC) and helicenic diastereomers. The agreement between theoretical and experimental spectra, including absorption (ABS, ECD) and emission (PL, CPL), is excellent, validating a quantitative interpretation of the spectral features on the basis of natural transition orbitals and TheoDore analyses. It is demonstrated that across the set of studied Re(I) diastereomers, the emission process in the case of NHC diastereomers is metal to ligand charge transfer in nature and is dominated by the easy-axis anisotropy of the emissive excited multiplet. On the contrary, in the cases of the helicenic diastereomers, the emission process is intra ligand charge transfer in nature and is dominated by the respective easy-plane anisotropy of the emissive excited multiplet. This affects remarkably the photoluminescent properties of the molecules in terms of PL and CPL spectral band shapes, spin-vibronic coupling, relaxation times, and the respective quantum yields. Spin-vibronic coupling effects are investigated at the level of the state-average complete active space self-consistent field in conjunction with quasi-degenerate second order perturbation theory. It is in fact demonstrated that a spin-vibronic coupling mechanism controls the observed photophysics of this class of Re(I) complexes.

Application of steady-state and time-resolved fluorescence spectroscopy in identification of cold-pressed vegetal oils

Monitoring the quality of food products is very important, due to the fact that substances potentially harmful to consumers may be formed during production and storage. In addition, vegetal oils are subject to falsification, which is based mainly on mixing and adding other, usually cheaper equivalents or providing false data on the composition and origin. In this way, the path from a very healthy product to a product that has a negative impact on the human body is very short. In this study fluorescence spectra and fluorescence decay kinetics of selected cold-pressed oils were characterized and the origin of the observed fluorescence bands was discussed. The obtained fluorescence characteristics were found to be the unique fingerprints of the individual oils and showed evident differences which arise from specific qualitative and quantitative compositions of the oils. The most apparent differences in the shape of fluorescence bands were observed in the emission spectrum at excitation wavelength 350 nm and in the excitation spectrum recorded at emission wavelength 500 nm. The obtained results show the utility of the applied steady-state and time –resolved fluorescence measurements in the identification of the tested vegetal oils.

Stereoselective Plasmonic Interaction in Peptide-tethered Photopolymerizable Diacetylenes Doped with Chiral Gold Nanoparticles.

Designing polymeric systems with ultra-high optical activity is instrumental in the pursuit of smart artificial chiroptical materials, including the fundamental understanding of structure/property relations. Herein, we report a diacetylene (DA) moiety flanked by chiral D- and L-FF dipeptide methyl esters that exhibits efficient topochemical photopolymerization in the solid phase to furnish polydiacetylene (PDA) with desired control over the chiroptical properties. The doping of the achiral gold nanoparticles provides plasmonic interaction with the PDAs to render asymmetric shape to the circular dichroism bands. With the judicious design of the chiral amino acid ligand appended to the AuNPs, we demonstrate the first example of selective chiral amplification mediated by stereo-structural matching of the polymer-plasmonic AuNP hybrid pairs. Such ordered self-assembly aided by topochemical polymerization in peptide-tethered PDA provides a smart strategy to produce soft responsive materials for applications in chiral photonics.

Parameterized model to approximate theoretical collision-induced absorption band shapes for O2-O2 and O2-N2

Collision-induced absorption from vibronic transitions of O2-O2 and O2-N2 collision complexes is an important contributor to light-matter interaction in the atmosphere with relevance to radiative heat transfer and remote sensing. Despite in-depth studies involving quantum calculations of this effect, comparisons between experiment and theory would benefit from less computationally burdensome calculations that closely approximate the temperature dependence of the theoretical band shape and intensity. Accordingly, we present a parameterized representation of recent quantum calculations for collision-induced absorption by O2-O2 and O2-N2 about the 1.27 μm monomer band of O2. This approach leverages the theoretical decomposition of the spectra into exchange and spin-orbit contributions, with each component having a distinct temperature-dependent band shape. Composite spectra are approximated as a linear combination of the theoretical profiles with seven adjustable parameters that scale the component intensities and their dependences on temperature. We demonstrate that this empirical representation can accurately simulate the theoretical calculations, and we present a global fit of the model to previously reported collision-induced absorption spectra (O2-O2, O2-N2, and O2-air) measured by cavity ring-down spectroscopy over the temperature range 271 K–332 K.

Infrared study of the structure of silicon oxynitride films produced by plasma enhanced chemical vapor deposition

The structure of thin (∼300nm) SiOxNy (0.23≤x≤1.95, 0.01≤y≤0.32) films produced by plasma enhanced chemical vapor deposition is studied by infrared (IR) spectroscopy. The dependence of the shape of the main IR absorption band in the range of 700–1400 cm–1 upon film composition is analyzed. The IR spectra exhibit strong overlapping of the bands corresponding to absorption on Si–O and Si–N bonds. A problem of separating these components is solved. Analysis of their relative intensities provides an insight into the film structure. The films with high oxygen content are found to have a homogeneous structure similar to that of nonstoichiometric Si oxide that can be described by the random bonding model. Increase of relative Si concentration and simultaneous decrease of oxygen and nitrogen content changes the film structure to the two-phase one obeying the random mixture model. Such material may be represented as a uniform mixture of interconnecting silicon–oxygen tetrahedra (Si–OaSi4-a, a=0..4) and silicon–nitrogen pyramids (Si3N). Relative Si concentration in the Si oxynitride films and their deposition temperature are hypothesized to play a decisive role on their structure, which is supported by thermodynamic modeling.

Anatomical variations of the calcaneofibular ligament in human foetuses

Ligaments anatomy often show a huge anatomy variations between species and individuals. For example calcaneofibular ligaments (CFL) characterize the great variability of morphological shape or presence of additional bands. The aim of this study was to propose first anatomical classification of CFL concerning on human fetuses. We investigated thirty spontaneously-aborted human fetuses aged 18–38 weeks of gestation at death. Sixty lower limbs (30 left and 30 right) fixed in 10% formalin solution were examined. The morphological variability of CFL was assessed. Four types of CFL morphology were observed. Type I was characterized by a band shape. This was the most common type, occurring in 53% of all cases. Based on our study we are proposing a classification based on four morphological types of CFL. Types 2 and 4 are further divided into subtypes. Present classification may be useful to better understand the anatomical development of ankle joint.

Temperature Dependences of IR Spectral Bands of Humic Substances of Silicate-Based Soils

Temperature-dependent IR spectroscopy capable of revealing specific changes in the band intensities, positions, and shape was used to increase the information on humic substances (HS) from soils. Temperature dependences of IR spectra of HS isolated from silicate-based soils differing in the contents and nature of organic matter, chernozem and soddy podzolic soil, were investigated by attenuated total internal reflection FTIR in the mid-IR region (4000–400 cm−1) in the air within the moderate temperature range of 25–215 °C (298–488 K) with a step of 2.5 °C. The dependences of shifts in frequency (wavenumber) corresponding to band maxima and integrated band intensities were built for all major bands. Observed reversible frequency shifts upon heating and cooling can be interpreted as forming structures in the dry state. The behavior of integrated intensities of bands assigned to C–H and C–C vibrations, characteristic vibrations of polyaromatic compounds, carboxylic acids, and carboxylates were shown, and similar behavior for the same group (symmetric and antisymmetric stretches) were revealed. Differences in the temperature trends in chernozem and soddy podzolic soils due to different structures (aliphatic and aromatic) and functional groups (carboxylic and carboxylate) are shown. The different behavior of the bands corresponding to carboxylic groups and skeletal vibrations differentiates soil types with different organic matter. The temperature trends of band maximum and intensity shifts are less prone to measurement conditions and may serve as qualitative parameters characterizing the composition of soil humic substances.

INFLUENCE OF SOLID LIQUID STATES RATIOS ON THE COMPOSITION AND PROPERTIES OF HUMATE-CONTAINING ORGANO-MINERAL FERTILIZERS

Human economic activity leads to removal of nutrients from the soil along with the crop. Nutrients losses also occur because of natural processes (erosion, leaching, etc.). It is necessary to replenish the missing nutrients with the use of humate-containing organomineral fertilizers to preserve soil fertility and increase productivity. The purpose of this work is to study the processes of iron (III) phosphates interaction with potassium humate and to obtain humate-containing organomineral fertilizers. Methodology. Chemical analysis, infrared spectroscopy, X-ray phase analysis methods have been used. Results and discussion. The processes of obtaining humate-containing organomineral fertilizers by the interaction in the systems “iron dihydrogen phosphate - potassium humate”, “iron hydrogen phosphate - potassium humate” and “iron orthophosphate - potassium humate” have been studied. It has been determined that an increase in the S:L ratio from 1:3 to 1:6 leads to an increase in the content of the digestible forms of Р2О5 up to 44.70%, nitrogen up to 1.85% and the output of humic substances up to 79.23%. An analysis of the IRS data indicates the multicomponentness and complexity of the composition of humate-containing organomineral fertilizers samples. Conclusion. It has been shown that the absorption bands of humic compounds of various functional groups and various substitutions phosphates are superimposed, while the shape of the absorption bands distorted, and their maxima have shifted to the high- or low-frequency area. It has been found that, regardless the phosphate ionnature, an increase in the ratio of S:L leads to a decrease in the absolute content of total, water-soluble and assimilable forms of P2O5. Concurrently, the phosphate part almost completely converted into the assimilated form. It has been defined that adding of the potassium humate, makes all phosphorus, which is in the indigestible form in the iron phosphates, almost completely pass into a mobile and assimilable form. It has been revealed that the addition of potassium humate into the systems with iron phosphates of various degrees of substitution makes it possible to neutralize the residual acidity of the pulp, and the neutralization process proceeds without P2O5 retrogradation. The resulting products have good physical, mechanical and fertilizer properties.

Band Structure Evolution during Reversible Interconversion between Dirac and Standard Fermions in Organic Charge-Transfer Salts

Materials containing Dirac fermions (DFs) have been actively researched because they often alter electrical and magnetic properties in an unprecedented manner. Although many studies have suggested the transformation between standard fermions (SFs) and DFs, the non-availability of appropriate samples has prevented the observation of the transformation process. We observed the interconversion process of DFs and SFs using organic charge-transfer (CT) salts. The samples are unique in that the constituents (the donor D and acceptor A species) are particularly close to each other in energy, leading to the temperature- and D-A-combination-sensitive CT interactions in the solid states. The three-dimensional weak D–A CT interactions in low-symmetry crystals induced the continuous reshaping of flat-bottomed bands into Dirac cones with decreasing temperature; this is a characteristic shape of bands that converts the behavior of SFs into that of DFs. Based on the first-principles band structures supported by the observed electronic properties, round-apex-Dirac-cone-like features appear and disappear with temperature variation. These band-structure snapshots are expected to add further detailed understanding to the related research fields.

Infrared Spectroscopic Investigations of Calcium Oxalate Monohydrate (Whewellite) Dehydration/Rehydration

Variable-temperature infrared spectroscopy is employed to monitor molecular vibrations during dehydration of calcium oxalate monohydrate (COM) and hydration of anhydrous calcium oxalate (COA). A unique variable-temperature infrared spectroscopy approach combines precise sample temperature control and rapid (2 °C s−1) heating/cooling with high-sensitivity infrared analysis. Infrared spectra are obtained at specific isothermal sample temperatures, while applying linear temperature versus time heating and cooling ramps, and in coordination with programmed temperature steps. Spectrum vibration bands provide information regarding the symmetry and local environments of solid-state water molecules and oxalate anions. When COM is heated, water molecules liberated from different crystallographic sites are selectively detected. Subtle oxalate anion configuration changes associated with water losses are detected based on infrared vibration band shapes and wavenumber trends. Dehydration and rehydration processes occur at lower temperatures and over narrower temperature ranges than conventional thermal analysis methods because samples consist of thin layers of small particles. Reversible and irreversible sample changes are distinguished by using a step heating/cooling temperature program and spectral subtractions. COA temperature-dependent structure variations that occur while heating and cooling samples in an atmosphere with a low water vapor concentration are characterized.

Exploring the suitability of narrow-bandgap compounds for thermoelectric application

Different opinion exists regarding the role of bandgap size on thermoelectric variables. Motivated by the observation that the band shape can in a definite way affect thermoelectric properties, two compounds (BaSiSr and IrBiZr) have been evaluated for optimum thermoelectric application. The phonon spectrum, band structure, mechanical and thermoelectric properties of the two compounds were investigated using the density functional theory. The calculated bandgap size of the compounds are comparable (IrBiZr = 0.223 eV; BaSiSr = 0.220 eV). The valence energy edge peaked at the Fermi level for both compounds. The highest valence energy edge occurred at a single high symmetry point (Γ for IrBiZr) but at two symmetry points (X and W for BaSiSr). IrBiZr gave an overall superior performance over BaSiSr in the calculated elastic, thermodynamic and thermoelectric parameters. A lesser role for bandgap size can therefore be indicated in the design and optimization of novel thermoelectric materials in view of better results in favor of IrBiZr than BaSiSr.

The behavior of water molecules in the nanocavities of the HKUST-1 framework: A combined quantum mechanical and vibrational spectroscopy investigation

We have investigated the host/guest molecular interactions and the H-bonding clustering in the H2O/HKUST-1 system. In-situ Fourier transform infrared spectroscopy was the experimental technique used to gather information at the molecular level. Measurements collected under sorption equilibrium conditions and in a dynamic regime were interpreted with the aid of a detailed QM vibrational analysis of the host/guest adduct and of a series of H2O clusters. The local arrangement of the adduct formed by H2O and the coordinatively unsaturated sites was characterized in terms of structure and interaction energy, and signatures for this adduct were predicted by theory in the ν(OH) range and experimentally confirmed. Within the metal organic framework nanocavities, six-membered water clusters having specific conformations were found to be the prevailing species. Cyclic trimers were also identified, their stabilization being ascribed to nanoconfining effects. The analysis of the δ(HOH) range elucidated the nature of the complex band shape and confirmed the results obtained in the ν(OH) interval. Low-temperature measurements allowed us to exclude the crystallization of the water clusters in the nanocavities.

Impact of electron correlations on the k-resolved electronic structure of PdCrO2 revealed by Compton scattering

Delafossite PdCrO2 is an intriguing material which displays nearly-free electron and Mott insulating behaviour in different layers. Both angle-resolved photoemission spectroscopy (ARPES) and Compton scattering measurements have established a hexagonal Fermi surface in the material’s paramagnetic phase. However, the Compton experiment detected an additional structure in the projected occupancy which was originally interpreted as an additional Fermi surface feature not seen by ARPES. Here, we revisit this interpretation of the Compton data. State-of-the-art density functional theory (DFT) with dynamical mean field theory (DMFT), the so-called DFT+DMFT method, predicts the Mott insulating state along with a single hexagonal Fermi surface in excellent agreement with ARPES and Compton. However, DFT+DMFT fails to predict the intensity of the additional spectral weight feature observed in the Compton data. We infer that this discrepancy may arise from the DFT+DMFT not being able to correctly predict certain features in the shape and dispersion of the unoccupied quasiparticle band near the Fermi level. Therefore, a theoretical description beyond our DFT+DMFT model is needed to incorporate vital electron interactions, such as inter-layer electron coupling interactions which for PdCrO2 gives rise to the Kondo-like so-called intertwined excitation.

Photoluminescence and cathodoluminescence of CaCu(Si[formula omitted]O[formula omitted])[formula omitted

Photoluminescence, cathodoluminescence and light absorption spectra of CaCu(Si2O5)2 have been explored in the spectral range from ultraviolet to near infrared. The luminescence and light absorption spectral bands have been analyzed to determine their constituent peaks. In photoluminescence spectra, the main very intense luminescence band reaching maximum around the quantum energy of 1.42 eV has been found to be composed of six spectral components with the strongest one peaked near 1.41 eV. In cathodoluminescence, only three of six lines have been found to constitute this band, with the strongest one peaking also at 1.41 eV. Besides, two much weaker bands of cathodoluminescence—a narrower one peaked at about 2.2 eV and a broad one spreading from the blue–green spectral region to the near UV range—have been detected in the visible and UV spectral ranges at T=300 and 80 K and the e-beam energies of 10, 15 and 30 keV. The shape and peak composition of the latter band depend on the e-beam energy and sample temperature. The origin of the derived spectral peaks is discussed.

The Problem of CO2 Reabsorption in Emission Spectra

The authors present a detailed explanation for selective reabsorption by the CO2 ν3-band when passing its optical emission through an atmospheric-pressure air column (60 cm long, 410 ppm CO2) connecting a microwave-discharge cell and the entrance window of a high-resolution Fourier Transform spectrometer. The CO2 band shapes are explained with a two-temperature model of emission and foreground absorption. Selective CO2 atmospheric reabsorption is a common effect in optical emission measurements. It primarily affects the fundamental infrared bands, which comprise the main part of the missing laboratory emission and must be taken into account in (exo)planetary atmospheric models.

Band structure of a nonparabolic two-dimensional electron gas system

Using angle-resolved photoelectron spectroscopy (ARPES), we study the band structures of two-dimensional electron gases (2DEGs) formed at Te-doped surfaces of InAs(110), as a result of band bending. The selected surface system is very clean and stable; therefore, ARPES spectra may be registered in short times, with minimal adsorption of residual gases and no photon beam-induced damage. We record a set of data that allows for a detailed analysis of the 2DEG band shapes, their thermal dependencies, and for an assessment of the many-body interactions. We find the electron-phonon interaction extremally weak and the electron-electron interactions hidden in dominant electron-donor interactions. While 2DEG band shapes are observed to be variable in correlation with the 2DEG density, this is tracked down to the variability of the band-bending potential and nonparabolicity of the system, and not to the many-body interactions. Thus, many-body renormalization of the 2DEG bands is not required, and the bands are described well by using the one-electron theoretical frame.

Designable mechanical properties of modified body-centered cubic lattice materials

Lattice materials possess broad application potential in many engineering fields due to their excellent mechanical properties. In this paper, a thorough investigation is carried out for the lattice materials with the generalized body-centered cubic (BCC) cell geometry. The investigated geometry variations include (1) adding additional reinforcement bars along several cell edges, and (2) offsetting the central vertex of the cubic cell that the oblique beams connect. The influences of the cell geometry on the stiffness, the Poisson’s ratio, the energy absorption capacity and the deformation pattern of the generalized cubic lattice are ascertained through extensive theoretical and finite element (FE) numerical analyses. The results indicate that adding reinforcement bars along the loading direction can effectively enhance the stiffness and strength, but does not significantly change the deformation pattern as depicted by the shape of shear bands. The additional bars perpendicular to the loading direction can largely influence the Poisson’s ratio, making it possible to approach unity. It is found that a modified BCC lattice with properly offset central cell vertices achieves an optimal energy absorption capacity that is about 2.26 times of traditional BCC lattice. This work could provide a comprehensive reference for the mechanical properties of the most generalized BCC lattice materials.

An Expedited Route to Optical and Electronic Properties at Finite Temperature via Unsupervised Learning.

Electronic properties and absorption spectra are the grounds to investigate molecular electronic states and their interactions with the environment. Modeling and computations are required for the molecular understanding and design strategies of photo-active materials and sensors. However, the interpretation of such properties demands expensive computations and dealing with the interplay of electronic excited states with the conformational freedom of the chromophores in complex matrices (i.e., solvents, biomolecules, crystals) at finite temperature. Computational protocols combining time dependent density functional theory and ab initio molecular dynamics (MD) have become very powerful in this field, although they require still a large number of computations for a detailed reproduction of electronic properties, such as band shapes. Besides the ongoing research in more traditional computational chemistry fields, data analysis and machine learning methods have been increasingly employed as complementary approaches for efficient data exploration, prediction and model development, starting from the data resulting from MD simulations and electronic structure calculations. In this work, dataset reduction capabilities by unsupervised clustering techniques applied to MD trajectories are proposed and tested for the ab initio modeling of electronic absorption spectra of two challenging case studies: a non-covalent charge-transfer dimer and a ruthenium complex in solution at room temperature. The K-medoids clustering technique is applied and is proven to be able to reduce by ∼100 times the total cost of excited state calculations on an MD sampling with no loss in the accuracy and it also provides an easier understanding of the representative structures (medoids) to be analyzed on the molecular scale.

Cost-Effective Simulations of Vibrationally-Resolved Absorption Spectra of Fluorophores with Machine-Learning-Based Inhomogeneous Broadening.

The results of electronic and vibrational structure simulations are an invaluable support for interpreting experimental absorption/emission spectra, which stimulates the development of reliable and cost-effective computational protocols. In this work, we contribute to these efforts and propose an efficient first-principle protocol for simulating vibrationally-resolved absorption spectra, including nonempirical estimations of the inhomogeneous broadening. To this end, we analyze three key aspects: (i) a metric-based selection of density functional approximation (DFA) so to benefit from the computational efficiency of time-dependent density function theory (TD-DFT) while safeguarding the accuracy of the vibrationally-resolved spectra, (ii) an assessment of two vibrational structure schemes (vertical gradient and adiabatic Hessian) to compute the Franck-Condon factors, and (iii) the use of machine learning to speed up nonempirical estimations of the inhomogeneous broadening. In more detail, we predict the absorption band shapes for a set of 20 medium-sized fluorescent dyes, focusing on the bright ππ★ S0 → S1 transition and using experimental results as references. We demonstrate that, for the studied 20-dye set which includes structures with large structural variability, the preselection of DFAs based on an easily accessible metric ensures accurate band shapes with respect to the reference approach and that range-separated functionals show the best performance when combined with the vertical gradient model. As far as band widths are concerned, we propose a new machine-learning-based approach for determining the inhomogeneous broadening induced by the solvent microenvironment. This approach is shown to be very robust offering inhomogeneous broadenings with errors as small as 2 cm-1 with respect to genuine electronic-structure calculations, with a total CPU time reduced by 98%.