Absorption Spectra Research Articles

Empirical Modal Decomposition Combined with Deep Learning for Photoacoustic Spectroscopy Detection of Mixture Gas Concentrations.

In photoacoustic spectroscopy based multicomponent gas analysis, the overlap of the absorption spectra among different gases can affect the measurement accuracy of gas concentrations. We report a multicomponent gas analysis method based on empirical modal decomposition (EMD), convolutional neural networks (CNN), and long short-term memory (LSTM) networks that can extract the exact concentrations of mixed gases from the overlapping wavelength-modulated spectroscopy with second harmonic (WMS-2f) detection. The WMS-2f signals of 25 different concentration combinations of acetylene-ammonia mixtures are detected using a single distributed feedback laser (DFB) at 1531.5 nm. The acetylene concentrations range from 2.5 to 7.5 ppm and the ammonia concentrations from 12.5 to 37.5 ppm. The data set is enhanced by cyclic shifting and adding Gaussian noise. The classification accuracy of the test set reaches 99.89% after tuning. The mean absolute errors of the five additional sets of data measured under different conditions are 0.092 ppm for acetylene and 1.902 ppm for ammonia, within the above concentration ranges.

Metallic Ca Aggregates Formed Along Ion Tracks and Optical Anisotropy in CaF2 Crystals Irradiated with Swift Heavy Ions

It is known that swift heavy ion (SHI) irradiation induces the shape elongation of metal nanoparticles (NPs) embedded in transparent insulators, which results in anisotropic optical absorption. Here, we report another type of the optical anisotropy induced in CaF2 crystals without including intentionally embedded metal NPs. The CaF2 samples were irradiated with 200 MeV Xe14+ ions with an incident angle of 45° from the surface normal. With the increasing fluence, an absorption band at ~550 nm, which is ascribed to Ca aggregates, increases both the intensity and the anisotropy. XTEM observation clarified the formation of the continuous line structures and the discontinuous NP chains parallel to the SHI beam. Numerical simulations of the optical absorption spectra suggested the NP chains but not the continuous line structures as the origin of the anisotropy. The optical anisotropy in CaF2 irradiated with SHIs is different from the shape elongation of NPs.

Distance-dependent symmetry-breaking charge transfer in 9,10-bis(phenylethynyl)anthracene dimers.

To investigate the effect of the through-bond coupling strength on the symmetry-breaking charge separation (SB-CS) dynamics and mechanism, three 9,10-bis((4-hexylphenyl)ethynyl)anthracene dimers with varying distances, viz., a single-bond linked dimer (0-dimer), a phenylene linked dimer (1-dimer) and a para-biphenylene linked dimer (2-dimer), were synthesized and studied systematically using steady-state and transient spectroscopy. Steady-state absorption spectra revealed that the electronic coupling strength decreased gradually with the increase of the inter-chromophore distance, and the transition of S0→S1 includes the dark charge transfer (CT) excitation. fs-TA spectra demonstrated that SB-CS could be conducted in both weakly and highly polar solvents for 0-dimer, but the SB-CS dynamics has a significant difference. In weakly polar solvents, SB-CS only produces the partial CT (PCT) state, but it could generate the CT state via the PCT state in highly polar solvent. In comparison, SB-CS is only proceeded in highly polar solvents in 1-dimer and 2-dimer to produce the CT state directly. These results demonstrate that the SB-CS dynamics is strongly dependent on the inter-chromophore electronic coupling, and the relatively strong electronic coupling is crucial for the occurrence of SB-CS in weakly polar environment that is commonly presented in photoelectric devices.

Impact of the host lattice on crystallographic, Raman, optical, and luminescent properties on the terbium ion

AbstractA comparative study of the Gd2O3:Tb and Y2O3:Tb nanoparticles (NPs) was presented to examine the influence of the host lattices on the crystallographic phase, surface characteristics, optical properties, Raman effect, and photoluminescence properties. Cubic shapes Gd2O3:Tb and Y2O3:Tb NPs with an estimated crystalline size of 17 and 11 nm were recorded from the X‐ray diffraction pattern, respectively. Comparative absorption spectra of both oxides NPs were presented to examine the dispersibility, colloidal stability, and optical behavior of the NPs. Energy bandgap values were estimated to monitor the optical characteristics of the metal oxides in the UV/Vis region. Fourier transform infrared was recorded to confirm the surface‐attached water and organic moieties. The Raman spectra of metal oxides were recorded to examine the symmetrical dis‐order and polarizability of the vibrational bands. The ionic radius of the atoms distorts the bond structure resulting in it greatly influenced the vibrational bands of the materials. The emission spectra certified the effective doping of the luminescent Tb3+‐ion in the metal oxide host lattices. Raman spectra and emission spectra validated the crystal symmetry imperfections; subsequently, the efficiency of the Raman active modes and emission transitions was greatly influenced. In a comparative analysis, Y2O3:Tb NPs exhibited higher luminescence intensity in comparison with the Gd2O3:Tb NPs.

Theoretical design of an electrically and thermally dual-controlled double-band absorber based on graphene and InSb

A novel, to our knowledge, double-band metamaterial absorber based on graphene and InSb is proposed in the terahertz regime. The amplitude and center frequency of the absorber can be electrically tuned by adjusting the graphene chemical potential and thermally controlled by varying the InSb temperature independently. First, owing to the bright–bright mode coupling effect, the average absorption rate of double-band absorber can reach 97% in the FDTD simulation. Meanwhile, the physical absorption mechanism can be analyzed theoretically by the radiating two-oscillator model. Second, when the chemical potential of graphene increases, the absorption rates of the absorber decrease gradually, and the absorption frequencies are almost unchanged. Moreover, if the temperature of InSb increases, the absorption frequencies and rates of absorber increase simultaneously. Finally, the impact of parameters on the absorption spectra, and the excellent sensing performance of the dual-band absorber as a refractive index sensor, are further discussed. This work provides a theoretical basis for the designs of dual-tunable absorbers and sensors.

Solvatochromic behavior on the absorption, transmittance and emission spectra for some organic dyes as active media

Solvatochromic behavior on the absorption, transmittance and emission spectra for some organic dyes as active media

Atmospheric propane (C3H8) column retrievals from ground-based FTIR observations in Xianghe, China

Abstract. Propane (C3H8) is an important trace gas in the atmosphere, as it is a proxy for oil and gas production and has a significant impact on atmospheric chemical reactions related to the hydroxyl radical and tropospheric ozone formation. In this study, solar direct absorption spectra near 2967 cm−1 recorded by a ground-based Fourier transform infrared spectrometer (FTIR) were applied to retrieve C3H8 total columns between June 2018 and July 2022 in Xianghe in north China. The systematic and random uncertainties of the C3H8 column retrieval are estimated to be 18.4 % and 18.1 %, respectively. The mean and standard deviation of the C3H8 columns derived from the FTIR spectra in Xianghe are 1.80 ± 0.81 (1σ) × 1015 molec. cm−2. Good correlations are found between C3H8 and other non-methane hydrocarbons, such as C2H6 (R=0.84) and C2H2 (R=0.79), as well as between C3H8 and CO (R=0.72). However, the correlation between C3H8 and CH4 is relatively weak (R=0.45). Moreover, the FTIR C3H8 measurements in Xianghe are also compared against MkIV measurements at several sites around the world. The new FTIR measurements in Xianghe provide us with insight into C3H8 column variations and the underlying processes in north China.

THz biosensing for early detection of influenza and coronaviruses using dielectric metamaterials

Abstract The world has faced a significant challenge since December 2019, when coronavirus (COVID-19) was found. Viruses of this type are causing pandemics all over the world right now. For this purpose, a biosensor is designed to operate based on metamaterial (MM) incorporated and can detect different coronaviruses. The proposed metamaterial absorber (MMA) includes two bands with perfect absorption characteristics and a narrow absorption bandwidth: 4.093 THz and 3.647 THz. The circuit model’s transmission line technique is another approach to verifying the absorber’s functionality. The proposed design consists of a square-shaped graphene ring (SGR) and a silicon-based square ring resonator (SSRR) to provide unique and narrow band absorption characteristics. Changing the graphene’s chemical potential suggests MMA tuneability and control capability. The suggested MMA can detect several coronaviruses because of its extremely narrow absorption spectrum behavior. It has unique features such as ultra-narrow absorption bandwidth, polarization insensitivity, and simplicity. The MMA is designed with a compact structure, good sensitivity (s), exceptional figure of Merit (FOM), and superior Quality factor (Q) values.

Effect of oxygen vacancies on enhancing the photo-catalytic activity, photo-luminescence and electronic structure properties of nanostructured Y-doped CeO2

The exceptional characteristics of CeO2 and Ce1-xYxO2 (x = 0.03, 0.05 and 0.07) nanoparticles were reported in the manuscript supporting that Y3+replaces Ce3+/Ce4+leads to oxygen vacancies formation. The results of XRD measurements revealed FCC structure of decreased crystallite size of CeO2 with improved crystallinity. To investigate the surface morphology, HRTEM and SAED patterns were performed. EDX analyses were undertaken to discuss the elemental and compositional characteristics. The absorption spectra using UV–Vis–NIR spectroscopy were analyzed and red shifted absorbance was found to enhance with decreasing band gap values for increased Y doping. The Photoluminescence spectra depicted various emissions representing the development of various defects and oxygen vacancy with incorporation of Y content in the lattice with CCT values below 4000 K to be classified as warm yellow light for indoor applications. The development of oxygen vacancies in the CeO2 lattice was further supported by XPS measurements for core levels Ce 3d, O 1s and Y 3d. Furthermore, the XPS measurements also reported the valence states of elements, Ce with 3+ and 4+, Y with 3+ and O with 2- along with charged oxygen vacancies. The photo-catalytic analysis revealed that Y-doped CeO2 nanoparticles show better degradation using a variety of characterization. A degradation mechanism that illustrates the impact of oxygen vacancies created by Y-doping on the photo-degradation process has been proposed. The novelty of Y-doped CeO2 nanoparticles stems from their improved photo-catalytic activities, which are linked to structural changes and the formation of oxygen vacancies. This doping considerably affects the electrical structure, resulting in better light absorption and less electron-hole recombination. The detailed outcomes of present study suggested the use of Y-doped CeO2 nanoparticles in optoelectronics, spintronics devices and photo-catalyst applications.

Synthesis, characterization, and study of linear and non-linear optical properties of some newly thieno[2,3-b]thiophene analogs

Abstract Newly 3,4-Diaminothieno[2,3-b]thiophene derivatives were synthesized by attaching with different aromatic have rich electron. The resulted compounds have been investigated by FT-IR, NMR, elemental analysis, and optical absorption spectra. Comparison between these resulted compounds revealed oxoindolin-3-ylidene)amino)thieno[2,3-b]thiophene has the highest absorption peak intensity at ~ 696nm, thin films have been prepared by thermal evaporation technique and characterized by UV-Visible-NIR spectroscopy as well as the allied absorption, dielectric and dispersion parameters have been investigated and compared with other reported results. Obtained results indicated diethyl 3,4-bis(((E)-2-oxoindolin-3-ylidene)amino)thieno[2,3-b]thiophene-2,5-dicarboxylate and 3,4-bis(((E)-2-oxoindolin-3-ylidene)amino)thieno[2,3-b]thiophene-2,5-dicarbonitrile have manifested small band energy gap energy 1.95, 1.66 eV; respectively as a result of increasing conjugation and high absorption coefficient, make these compounds ideal for use in solar cell. The high nonlinear parameters such as refractive index and third-order nonlinear susceptibility of these organic compound thin films are significantly asymptotic compared with chalcogenide and oxide materials, making them suitable for nonlinear optical devices.

Synthesis, Structure, Spectral and Redox Properties of Phenoxazine Embedded Heteroporphyrins

A series of phenoxazine embedded heteroporphyrins containing one phenoxazine, two pyrroles and one heterocycle, such as furan, thiophene, selenophene and telluorophene, connected through four meso carbon atoms were synthesized by condensing one equivalent of phenoxazine‐based tripyrrane with one equivalent of the appropriate 2,5‐bis(hydroxymethyl‐p‐tolyl) heterocycle under acid‐catalyzed conditions, and their structure, spectral and electrochemical properties were compared with those of previously reported phenothiazine embedded heteroporphyrins. The X‐ray crystal structure of the phenoxazine embedded selenoporphyrin revealed that the selenophene ring, which is opposite phenoxazine moiety, points outward from the macrocyclic core, and the phenoxazine unit deviated by an angle of 39.47° from the mean plane defined by the four meso carbons atoms. The replacement of the phenothiazine unit in phenothiazine embedded heteroporphyrins with a phenoxazine unit led to significant alteration of the electronic properties of the macrocycles, as reflected in their spectral and electrochemical properties. The absorption spectra of phenoxazine embedded heteroporphyrins showed bathochromically shifted absorption bands, hypsochromically shifted fluorescence bands with decent quantum yields, more facile oxidation and more difficult reduction as compared to the corresponding phenothiazine embedded heteroporphyrins. DFT and TD‐DFT studies were in support of the experimental observations.

Enhanced UV-Visible Absorption of Silicon Solar Cells Utilizing YAG:Ce3+ and Ba5Si2O6Cl6: Eu2+ Based on Spectral Down-Shifting.

Spectral down-shifting materials can convert the less utilized photons in the solar spectrum into the portion that solar cells can fully utilize, providing an effective means of improving the efficiency of solar cells. In this work, the spectral down-shifting material Ba5Si2O6Cl6: Eu2+ (BSOC) was prepared by a high-temperature solid-state method. The fluorescence spectra indicate that the absorption spectrum of BSOC can cover the range of 210-500nm, and has a strong emission spectrum with a broadband of 410-650nm. The wider spectral characteristics make it convenient to utilize the solar spectrum efficiently. Additionally, the BSOC phosphors precisely compensate for the weak absorption of YAG: Ce3+ (YAG) phosphors below 425nm. The YAG and BSOC phosphors were mixed, and the hybrid material has a wider absorption range (200-540nm) compared to YAG or BSOC alone. Finally, the electrical properties of the packaged cells were tested, and the results showed that the packaged cells with hybrid materials had higher short-circuit current density and photoelectric conversion efficiency compared to YAG or BSOC alone. In addition, the efficiency of the packaged cells with hybrid materials increased from 19.54 to 20.08% compared with the bare cells, a relative increase of 2.760%.

Cyano-substituted Bis((benzothiophen-2-yl)pyridine) (acetylacetonate) iridium complexes for efficient and stable deep red organic light-emitting diodes emitting at 673 nm

This study explores the development of cyano-substituted bis((benzothiophen-2-yl)pyridine) (acetylacetonate) iridium complexes, specifically Ir(btpCN)2(acac), for use in efficient and stable deep red organic light-emitting diodes (OLEDs) emitting at 673 nm. The new emitter, Ir(btpCN)2(acac), was designed to achieve red-shifted emission through strategic cyano substitution at the meta-position of pyridine moiety of btp ligand, leveraging the favorable overlap between its emission spectrum and the absorption spectrum of the exciplex host composed of BCzPh and CN-T2T. The OLED devices employing Ir(btpCN)2(acac) as the emitter exhibited a peak external quantum efficiency (EQE) of 10.2 % and an emission wavelength of 673 nm. Significantly, these devices demonstrated superior operational stability, with a lifetime (LT50) of 190.8 h at an initial luminance of 200 cd m−2, which is among the highest reported for deep-red OLEDs in the literature. This remarkable stability is achieved without compromising the device performance, making Ir(btpCN)2(acac) a highly promising candidate for commercial applications. In addition, the straightforward synthesis process of Ir(btpCN)2(acac) further enhances its potential for widespread use. Overall, our findings highlight the potential of cyano-substituted Ir complexes for creating efficient, stable, and commercially viable deep-red OLEDs. The balanced performance of Ir(btpCN)2(acac) in terms of efficiency, stability, and ease of synthesis marks a significant advancement in the development of OLED technology suitable for phototherapy and other applications requiring reliable deep-red light sources.

Living Therapeutics for Synergistic Hydrogen-Photothermal Cancer Treatment by Photosynthetic Bacteria.

Hydrogen gas (H2) therapy, recognized for its inherent biosafety, holds significant promise as an anti-cancer strategy. However, the efficacy of H2 treatment modalities is compromised by their reliance on systemic gas administration or chemical reactions generation, which suffers from low efficiency, poor targeting, and suboptimal utilization. In this study, living therapeutics are employed using photosynthetic bacteria Rhodobacter sphaeroides for in situ H2 production combined with near-infrared (NIR) mediated photothermal therapy. Living R. sphaeroides exhibits strong absorption in the NIR spectrum, effectively converting light energy into thermal energy while concurrently generating H2. This dual functionality facilitates the targeted induction of tumor cell death and substantially reduces collateral damage to adjacent normal tissues. The findings reveal that integrating hydrogen therapy with photothermal effects, mediated through photosynthetic bacteria, provides a robust, dual-modality approach that enhances the overall efficacy of tumor treatments. This living therapeutic strategy not only leverages the therapeutic potential of both hydrogen and photothermal therapeutic modalities but also protects healthy tissues, marking a significant advancement in cancer therapy techniques.

Statistics of protein electrostatics.

Molecular dynamics simulations of a small redox-active protein plastocyanin address two questions. (i) Do protein electrostatics equilibrate to the Gibbsian ensemble? (ii) Do the electrostatic potential and electric field inside proteins follow the Gaussian distribution? The statistics of electrostatic potential and electric field are probed by applying small charge and dipole perturbations to different sites within the protein. Nonergodic (non-Gibbsian) sampling is detectable through violations of exact statistical rules constraining the first and second statistical moments (fluctuation-dissipation relations) and the linear relation between free-energy surfaces of the collective coordinate representing the Hamiltonian electrostatic perturbation. We find weakly nonergodic statistics of the electrostatic potential (simulation time of 0.4-1.0 μs) and non-Gibbsian and non-Gaussian statistics of the electric field. A small dipolar perturbation of the protein results in structural instabilities of the protein-water interface and multi-modal distributions of the Hamiltonian energy gap. The variance of the electrostatic potential passes through a crossover at the glass transition temperature Ttr ≃ 170 K. The dipolar susceptibility, reflecting the variance of the electric field inside the protein, strongly increases, with lowering temperature, followed by a sharp drop at Ttr. The linear relation between free-energy surfaces can be directly tested by combining absorption and emission spectra of optical dyes. It was found that the statistics of the electrostatic potential perturbation are nearly Gibbsian/Gaussian, with little deviations from the prescribed statistical rules. On the contrary, the (nonergodic) statistics of dipolar perturbations are strongly non-Gibbsian/non-Gaussian due to structural instabilities of the protein hydration shell.

Antidiabetic, anti-inflammatory, antioxidant, and cytotoxicity potentials of green-synthesized zinc oxide nanoparticles using the aqueous extract of Helichrysum cymosum

The current research involved the synthesis of zinc oxide nanoparticles (ZnO-NPs) using an aqueous extract of Helichrysum cymosum shoots, and subsequent characterization via different analytical methods, such as UV–Vis spectroscopy, Scanning electron microscope (SEM), Energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Transmission electron microscope (TEM), and zeta potential. The biological effects of the ZnO-NPs were then tested against C3A hepatocyte cells and L6 myocyte cell lines via series of analysis, including cytotoxicity, antioxidant, anti-inflammatory, and antidiabetic effect via enzymatic inhibition. The UV–Vis analysis showed a maximum absorption spectrum at 360, and the TEM analysis reveals a spherical and hexagonal structures, with an average dimension of 28.05–58.3 nm, and the XRD reveals a crystalline hexagonal structure. The zeta potential evaluation indicated that the ZnO-NPs are relatively stable at − 20 mV, and the FTIR analysis identified some important functional group associated with phenolics, carboxylic acid, and amides that are responsible for reducing and stabilizing the ZnO-NPs. The synthesized ZnO-NPs demonstrated cytotoxic effects on the cell lines at higher concentrations (125 µg/mL and 250 µg/mL), complicating the interpretation of the results of the inflammatory and antioxidant assays. However, there was a significant (p < 0.05) increase in the inhibitions of pancreatic lipase, alpha-glucosidase, and alpha-amylase, indicating beneficial antidiabetic effects.

Performance of chatbots in queries concerning fundamental concepts in photochemistry.

The advent of chatbots raises the possibility of a paradigm shift across society including the most technical of fields with regard to access to information, generation of knowledge, and dissemination of education and training. Photochemistry is a scientific endeavor with roots in chemistry and physics and branches that encompass diverse disciplines ranging from astronomy to zoology. Here, five chatbots have each been challenged with 13 photochemically relevant queries. The chatbots included ChatGPT 3.5, ChatGPT 4.0, Copilot, Gemini Advanced, and Meta AI. The queries encompassed fundamental concepts (e.g., "Why is the fluorescence spectrum typically the mirror image of the absorption spectrum?"), practical matters (e.g., "What is the inner filter effect and how to avoid it?"), philosophical matters ("Please create the most important photochemistry questions."), and specific molecular features (e.g., "Why are azo dyes non-fluorescent?"). The chatbots were moderately effective in answering queries concerning fundamental concepts in photochemistry but were glaringly deficient in specialized queries for dyes and fluorophores. In some instances, a correct response was embedded in verbose scientific nonsense whereas in others the entire response, while grammatically correct, was utterly meaningless. The unreliable accuracy makes present chatbots poorly suited for unaided educational purposes and highlights the importance of domain experts.

Investigation of linear and microscopic nonlinear optical responses of 1-indanone compounds in different environments based on polarity models

Molecular spectroscopic and nonlinear features can indicate positive changes by solvent molecules. In this work, DFT and spectroscopic techniques were used to study the polarity effects of different solvent environments. Polarity-based models were used for studying solvent induced interactions on the optical features of new groups of biomolecules. Despite the significant contribution of general effects on the molecular absorption spectra, there is considerable competition between general and specific environmental effects on the molecular emission properties. Under this condition, strong hydrogen bonds tend to increase molecular nonlinear responses. The same results were observed for the low order (first and second order) nonlinearity of biomolecules. Therefore, the studies on the environment effects on the biomolecules’ first order nonlinearity can give valuable information about higher-order optical responses. Moreover, 1-Indanone compounds with high nonlinearity can be considered as an effective element in designing optical devices.

Highly Accurate and Robust Constraint-Based Orbital-Optimized Core Excitations.

We adapt our recently developed constraint-based orbital-optimized excited-state method (COOX) for the computation of core excitations. COOX is a constrained density functional theory (cDFT) approach based on excitation amplitudes from linear-response time-dependent DFT (LR-TDDFT), and has been shown to provide accurate excitation energies and excited-state properties for valence excitations within a spin-restricted formalism. To extend COOX to core-excited states, we introduce a spin-unrestricted variant which allows us to obtain orbital-optimized core excitations with a single constraint. Using a triplet purification scheme in combination with the constrained unrestricted Hartree-Fock formalism, scalar-relativistic zero-order regular approximation corrections, and a semiempirical treatment of spin-orbit coupling, COOX is shown to produce highly accurate results for K- and L-edge excitations of second- and third-period atoms with subelectronvolt errors despite being based on LR-TDDFT, for which core excitations pose a well-known challenge. L- and M-edge excitations of heavier atoms up to uranium are also computationally feasible and numerically stable, but may require more advanced treatment of relativistic effects. Furthermore, COOX is shown to perform on par with or better than the popular ΔSCF approach while exhibiting more robust convergence, highlighting it as a promising tool for inexpensive and accurate simulations of X-ray absorption spectra.

Construction of Dual Electric Field Synergistic and Magnetic Recyclable SnFe2O4/ZnO Photocatalyst.

The recombination of photoinduced carriers hampers the photocatalysis process. Construction of the heterojunction and built-in piezoelectric field boosts the separation of electrons and holes. Herein, a novel magnetic recyclable SnFe2O4(SFO)/ZnO composite with enhanced photocatalytic performance based on the dual electric field synergism was proposed for the first time. This composite apparently alleviates the carrier recombination in SFO and extends the absorption spectrum of ZnO to the full spectrum. Consequently, 20%SFO/ZnO exhibits an excellent efficiency, which is 2.45 times that of ZnO and 4.61 times that of SFO, respectively. The differences in size and morphology between the SFO nanoparticles and the ZnO nanorods provide more contact areas, thus enlarging the deformation and enhancing the piezoelectric effect. The heterojunction and the piezoelectric field work together to modulate the transferring of carriers and elevate the photocatalytic activity. This design offers a plausible avenue for preparing efficient recyclable photocatalysts for application.