Showing papers on "Absorption spectroscopy published in 2017"

Molecular Optimization Enables over 13% Efficiency in Organic Solar Cells

Abstract: A new polymer donor (PBDB-T-SF) and a new small molecule acceptor (IT-4F) for fullerene-free organic solar cells (OSCs) were designed and synthesized The influences of fluorination on the absorption spectra, molecular energy levels, and charge mobilities of the donor and acceptor were systematically studied The PBDB-T-SF:IT-4F-based OSC device showed a record high efficiency of 131%, and an efficiency of over 12% can be obtained with a thickness of 100–200 nm, suggesting the promise of fullerene-free OSCs in practical applications

Fused Nonacyclic Electron Acceptors for Efficient Polymer Solar Cells.

Abstract: We design and synthesize four fused-ring electron acceptors based on 6,6,12,12-tetrakis(4-hexylphenyl)-indacenobis(dithieno[3,2-b;2′,3′-d]thiophene) as the electron-rich unit and 1,1-dicyanomethylene-3-indanones with 0–2 fluorine substituents as the electron-deficient units. These four molecules exhibit broad (550–850 nm) and strong absorption with high extinction coefficients of (2.1–2.5) × 105 M–1 cm–1. Fluorine substitution downshifts the LUMO energy level, red-shifts the absorption spectrum, and enhances electron mobility. The polymer solar cells based on the fluorinated electron acceptors exhibit power conversion efficiencies as high as 11.5%, much higher than that of their nonfluorinated counterpart (7.7%). We investigate the effects of the fluorine atom number and position on electronic properties, charge transport, film morphology, and photovoltaic properties.

Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source

Abstract: Time-resolved x-ray absorption spectroscopy (TR-XAS) has so far practically been limited to large-scale facilities, to subpicosecond temporal resolution, and to the condensed phase. We report the realization of TR-XAS with a temporal resolution in the low femtosecond range by developing a tabletop high-harmonic source reaching up to 350 electron volts, thus partially covering the spectral region of 280 to 530 electron volts, where water is transmissive. We used this source to follow previously unexamined light-induced chemical reactions in the lowest electronic states of isolated CF 4 + and SF 6 + molecules in the gas phase. By probing element-specific core-to-valence transitions at the carbon K-edge or the sulfur L-edges, we characterized their reaction paths and observed the effect of symmetry breaking through the splitting of absorption bands and Rydberg-valence mixing induced by the geometry changes.

Short-Wave Near-Infrared Linear Dichroism of Two-Dimensional Germanium Selenide

Abstract: Polarized detection has been brought into operation for optics applications in the visible band. Meanwhile, an advanced requirement in short-wave near-infrared (SW-NIR) (700–1100 nm) is proposed. Typical IV–VI chalcogenides—2D GeSe with anisotropic layered orthorhombic structure and narrow 1.1–1.2 eV band gap—potentially meets the demand. Here we report the unusual angle dependences of Raman spectra on high-quality GeSe crystals. The polarization-resolved absorption spectra (400–950 nm) and polarization-sensitive photodetectors (532, 638, and 808 nm) both exhibited well-reproducible cycles, distinct anisotropic features, and typical absorption ratios αy/αx ≈ 1.09 at 532 nm, 1.26 at 638 nm, and 3.02 at 808 nm (the dichroic ratio Ipy/Ipx ≈ 1.09 at 532 nm, 1.44 at 638 nm, 2.16 at 808 nm). Obviously, the polarized measurement for GeSe showed superior anisotropic response at around 808 nm within the SW-NIR band. Besides, the two testing methods have demonstrated the superior reliability for each other. For the...

Charge-Transfer-Induced Lattice Collapse in Ni-Rich NCM Cathode Materials during Delithiation

Abstract: Ni-rich LiNixCoyMnzO2 (NCM) cathode materials have great potential for application in next-generation lithium-ion batteries owing to their high specific capacity. However, they are subjected to severe structural changes upon (de)lithiation, which adversely affects the cycling stability. Herein, we investigate changes in crystal and electronic structure of NCM811 (80% Ni) at high states of charge by a combination of operando X-ray diffraction (XRD), operando hard X-ray absorption spectroscopy (hXAS), ex situ soft X-ray absorption spectroscopy (sXAS), and density functional theory (DFT) calculations and correlate the results with data from galvanostatic cycling in coin cells. XRD reveals a large decrease in unit cell volume from 101.38(1) to 94.26(2) A3 due to collapse of the interlayer spacing when x(Li) < 0.5 (decrease in c-axis from 14.469(1) A at x(Li) = 0.6 to 13.732(2) A at x(Li) = 0.25). hXAS shows that the shrinkage of the transition metal–oxygen layer mainly originates from nickel oxidation. sXAS, ...

Effects of oxygen vacancies on the structural and optical properties of β-Ga 2 O 3

Abstract: The structural, electronic, and optical properties of β-Ga2O3 with oxygen vacancies are studied by employing first-principles calculations based on density function theory. Based on the defects formation energies, we conclude the oxygen vacancies are most stable in their fully charge states. The electronic structures and optical properties of β-Ga2O3 are calculated by Generalized Gradient Approximation + U formalisms with the Hubbard U parameters set 7.0 eV and 8.5 eV for Ga and O ions, respectively. The calculated bandgap is 4.92 eV, which is consistent with the experimental value. The static real dielectric constants of the defective structures are increased compared with the intrinsic one, which is attributed to the level caused by the Ga-4s states in the bandgap. Extra peaks are introduced in the absorption spectra, which are related to Ga-4s and O-2p states. Experimentally, β-Ga2O3 films are deposited under different O2 volume percentage with ratio-frequency magnetron sputtering method. The measured results indicate that oxygen vacancies can induce extra emission peaks in the photoluminescence spectrum, the location of these peaks are close to the calculated results. Extra O2 can increase the formation energies of oxygen vacancies and thus reduce oxygen vacancies in β-Ga2O3.

Fabrication of Water-Soluble, Green-Emitting Gold Nanoclusters with a 65% Photoluminescence Quantum Yield via Host–Guest Recognition

Abstract: Metal nanoclusters (NCs) as a new type of fluorescent material have been extensively explored because of their attractive set of features such as their ultrafine size, low toxicity, and excellent photostability. However, little progress has been made in producing water-soluble, homogeneous, and ultrabright metal NCs. In this study, gold NCs (AuNCs) with a photoluminescence quantum yield (QY) as high as 65% are synthesized in water through a simple blending route. Weak emission is observed from the 6-aza-2-thiothymine-protected AuNCs (ATT-AuNCs); however, the fluorescence intensity can be prominently enhanced by introducing l-arginine (Arg) into the capping layer. The fluorescence enhancement mechanism is systematically investigated by the measurements of ultraviolet–visible absorption spectroscopy, photoluminescence spectroscopy, fluorescence lifetime spectroscopy, transmission electron microscopy, dynamic light scattering, X-ray photoelectron spectroscopy, 1H nuclear magnetic resonance, and calculations ...

Short-Wave Near-Infrared Linear Dichroism of Two-Dimensional Germanium Selenide

Abstract: Polarized detection has been brought into operation for optics applications in the visible band. Meanwhile, an advanced requirement in short-wave near-infrared (SW-NIR) (700–1100 nm) is proposed. Typical IV–VI chalcogenides—2D GeSe with anisotropic layered orthorhombic structure and narrow 1.1–1.2 eV band gap—potentially meets the demand. Here we report the unusual angle dependences of Raman spectra on high-quality GeSe crystals. The polarization-resolved absorption spectra (400–950 nm) and polarization-sensitive photodetectors (532, 638, and 808 nm) both exhibited well-reproducible cycles, distinct anisotropic features, and typical absorption ratios αy/αx ≈ 1.09 at 532 nm, 1.26 at 638 nm, and 3.02 at 808 nm (the dichroic ratio Ipy/Ipx ≈ 1.09 at 532 nm, 1.44 at 638 nm, 2.16 at 808 nm). Obviously, the polarized measurement for GeSe showed superior anisotropic response at around 808 nm within the SW-NIR band. Besides, the two testing methods have demonstrated the superior reliability for each other. For the...

Preparation of Monolayer MoS 2 Quantum Dots using Temporally Shaped Femtosecond Laser Ablation of Bulk MoS 2 Targets in Water.

Abstract: Zero-dimensional MoS2 quantum dots (QDs) possess distinct physical and chemical properties, which have garnered them considerable attention and facilitates their use in a broad range of applications. In this study, we prepared monolayer MoS2 QDs using temporally shaped femtosecond laser ablation of bulk MoS2 targets in water. The morphology, crystal structures, chemical, and optical properties of the MoS2 QDs were characterized by transmission electron microscopy, X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, UV-vis absorption spectra, and photoluminescence spectra. The analysis results show that highly pure, uniform, and monolayer MoS2 QDs can be successfully prepared. Moreover, by temporally shaping a conventional single pulse into a two-subpulse train, the production rate of MoS2 nanomaterials (including nanosheets, nanoparticles, and QDs) and the ratio of small size MoS2 QDs can be substantially improved. The underlying mechanism is a combination of multilevel photoexfoliation of monolayer MoS2 and water photoionization-enhanced light absorption. The as-prepared MoS2 QDs exhibit excellent electrocatalytic activity for hydrogen evolution reactions because of the abundant active edge sites, high specific surface area, and excellent electrical conductivity. Thus, this study provides a simple and green alternative strategy for the preparation of monolayer QDs of transition metal dichalcogenides or other layered materials.

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study

Abstract: Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Investigation on the broadband electromagnetic wave absorption properties and mechanism of Co3O4-nanosheets/reduced-graphene-oxide composite

Abstract: A cobaltosic-oxide-nanosheets/reduced-graphene-oxide composite (CoNSs@RGO) was successfully prepared as a light-weight broadband electromagnetic wave absorber. The effects of the sample thickness and amount of composite added to paraffin samples on the absorption properties were thoroughly investigated. Due to the nanosheet-like structure of Co3O4, the surface-to-volume ratio of the wave absorption material was very high, resulting in a large enhancement in the absorption properties. The maximum refection loss of the CoNSs@RGO composite was–45.15 dB for a thickness of 3.6 mm, and the best absorption bandwidth with a reflection loss below–10 dB was 7.14 GHz with a thickness of 2.9 mm. In addition, the peaks of microwave absorption shifted towards the low frequency region with increasing thickness of the absorbing coatings. The mechanism of electromagnetic wave absorption was attributed to impedance matching of CoNSs@RGO as well as the dielectric relaxation and polarization of RGO. Compared to previously reported absorbing materials, CoNSs@RGO showed better performance as a lightweight and highly efficient absorbing material for application in the high frequency band.

The Role of Electronic and Phononic Excitation in the Optical Response of Monolayer WS2 after Ultrafast Excitation

Abstract: Transient changes of the optical response of WS2 monolayers are studied by femtosecond broadband pump–probe spectroscopy. Time-dependent absorption spectra are analyzed by tracking the line width broadening, bleaching, and energy shift of the main exciton resonance as a function of time delay after the excitation. Two main sources for the pump-induced changes of the optical response are identified. Specifically, we find an interplay between modifications induced by many-body interactions from photoexcited carriers and by the subsequent transfer of the excitation to the phonon system followed by cooling of the material through the heat transfer to the substrate.

Coherent structural trapping through wave packet dispersion during photoinduced spin state switching

Abstract: The description of ultrafast nonadiabatic chemical dynamics during molecular photo-transformations remains challenging because electronic and nuclear configurations impact each other and cannot be treated independently. Here we gain experimental insights, beyond the Born-Oppenheimer approximation, into the light-induced spin-state trapping dynamics of the prototypical [Fe(bpy)3](2+) compound by time-resolved X-ray absorption spectroscopy at sub-30-femtosecond resolution and high signal-to-noise ratio. The electronic decay from the initial optically excited electronic state towards the high spin state is distinguished from the structural trapping dynamics, which launches a coherent oscillating wave packet (265 fs period), clearly identified as molecular breathing. Throughout the structural trapping, the dispersion of the wave packet along the reaction coordinate reveals details of intramolecular vibronic coupling before a slower vibrational energy dissipation to the solution environment. These findings illustrate how modern time-resolved X-ray absorption spectroscopy can provide key information to unravel dynamic details of photo-functional molecules.

IR spectroscopic investigations of chemical and photochemical reactions on metal oxides: bridging the materials gap

Abstract: In this review, we highlight recent progress (2008–2016) in infrared reflection absorption spectroscopy (IRRAS) studies on oxide powders achieved by using different types of metal oxide single crystals as reference systems. Precise polarization- and azimuth-dependent IRRAS data recorded for single crystal substrates has allowed for fundamental insights into the surface chemistry and photochemistry of numerous probe molecules on various surfaces exposed by three very important metal oxides (ZnO, TiO2, and CeO2). When using carbon monoxide (CO) as a probe molecule, deep insight into the role of defects in the surface chemistry of oxides can be gained, as will be demonstrated by the characterization of different imperfections (e.g., O vacancies, nanofacets) present at oxidic samples. In addition, photostimulated excitations, e.g., electron or hole polaronic trap states, can be studied using IR-spectroscopy. Reliable and comprehensive reference data acquired for different oxide monocrystal model systems enables atomic-level insights into the structural, electronic, and reactive properties of the substantially more complex nanostructured oxide particles. We foresee that future application of IR spectroscopy to other challenging systems, including polar oxide surfaces with their often complex reconstruction patterns and oxide-supported highly dispersed metal particles, will provide a major advancement in the understanding of heterogeneous catalysts (539 references).

Benzo-Fused Double [7]Carbohelicene: Synthesis, Structures, and Physicochemical Properties

Abstract: A benzo-fused double [7]carbohelicene (D7H) was synthesized through a regioselective cyclodehydrogenation of a tetranaphthyl-p-terphenyl-based precursor. The twisted (D7H-1) and anti-folded (D7H-2) conformers of D7H were separated by recrystallization, and their double helicene structures with overlapping terminal benzene rings were unambiguously elucidated by X-ray crystallography. A record-high isomerization barrier (46.0 kcal mol−1) in double helicenes was estimated based on density functional theory (DFT) calculation, which resulted in the excellent conformational stability of D7H. The physicochemical properties of D7H-1 and D7H-2 were investigated by UV/Vis absorption spectroscopy and cyclic voltammetry, displaying the variation of electronic structure upon conformational changes. The optical resolution of the racemic D7H-1 was carried out by chiral HPLC, offering enantiopure D7H-1-(P,P) and D7H-1-(M,M), which were further characterized by circular dichroism spectroscopy.

Mid-infrared dual-comb spectroscopy with electro-optic modulators

Abstract: Absorption spectroscopy of fundamental ro-vibrational transitions in the mid-infrared region provides a powerful tool for studying the structure and dynamics of molecules in the gas phase and for sensitive and quantitative gas sensing. Laser frequency combs permit novel approaches to perform broadband molecular spectroscopy. Multiplex dual-comb spectroscopy without moving parts can achieve particularly high speed, sensitivity and resolution. However, achieving Doppler-limited resolution in the mid-infrared still requires overcoming instrumental challenges. Here we demonstrate a new approach based on difference-frequency generation of frequency-agile near-infrared frequency combs that are produced using electro-optic modulators. The combs have a remarkably flat intensity distribution, and their positions and line spacings can be freely selected by simply dialing a knob. Using the proposed technique, we record, in the 3-μm region, Doppler-limited absorption spectra with resolved comb lines within milliseconds, and precise molecular line parameters are retrieved. Our technique holds promise for fast and sensitive time-resolved studies of, for example, trace gases.

Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption

Abstract: Many photoinduced processes including photosynthesis and human vision happen in organic molecules and involve coupled femtosecond dynamics of nuclei and electrons Organic molecules with heteroatoms often possess an important excited-state relaxation channel from an optically allowed ππ* to a dark nπ* state The ππ*/nπ* internal conversion is difficult to investigate, as most spectroscopic methods are not exclusively sensitive to changes in the excited-state electronic structure Here, we report achieving the required sensitivity by exploiting the element and site specificity of near-edge soft X-ray absorption spectroscopy As a hole forms in the n orbital during ππ*/nπ* internal conversion, the absorption spectrum at the heteroatom K-edge exhibits an additional resonance We demonstrate the concept using the nucleobase thymine at the oxygen K-edge, and unambiguously show that ππ*/nπ* internal conversion takes place within (60 ± 30) fs High-level-coupled cluster calculations confirm the method’s impressive electronic structure sensitivity for excited-state investigations Many photo-induced processes such as photosynthesis occur in organic molecules, but their femtosecond excited-state dynamics are difficult to track Here, the authors exploit the element and site selectivity of soft X-ray absorption to sensitively follow the ultrafast ππ*/nπ* electronic relaxation of hetero-organic molecules

Impact of White Light Illumination on the Electronic and Chemical Structures of Mixed Halide and Single Crystal Perovskites

Abstract: This study investigates the effect of white light illumination on the electronic and chemical properties of mixed halide perovskite (CH3NH3PbI3−xClx) thin films and CH3NH3PbI3 single crystals using photoelectron and absorption spectroscopy. The pristine materials' surfaces are found to be n-type because of surface band bending due to the presence of donor levels, likely consisting of reduced lead (Pb0) that acts as surface traps. When illuminating the sample with white light (up to 1 sun), the valence features shifted to lower binding energy due to surface photovoltage, i.e., the bulk of the materials is much less n-type. However, the surface photovoltage is only partially reversible and vanishes for prolonged illumination time. Concomitantly, a high concentration of metallic Pb0 is found, which induces strong Fermi-level pinning and quenching of the surface photovoltage. This is accompanied also by the formation of PbI2 defects. Similar experiments on single crystals reveal the presence of a high concentration of reduced (metallic) Pb0 at the sample surface after cleaving. The present findings indicate that the chemical and electronic properties of perovskite films are very sensitive to white light illumination. Accounting for these light-induced material changes is important to fully understand its photophysical properties and for improving the lifetime of perovskite-based devices.

Few-Layer Black Phosphorus Carbide Field-Effect Transistor via Carbon Doping.

Abstract: Black phosphorus carbide (b-PC) is a new family of layered semiconducting material that has recently been predicted to have the lightest electrons and holes among all known 2D semiconductors, yielding a p-type mobility (≈105 cm2 V-1 s-1 ) at room temperature that is approximately five times larger than the maximum value in black phosphorus. Here, a high-performance composite few-layer b-PC field-effect transistor fabricated via a novel carbon doping technique which achieved a high hole mobility of 1995 cm2 V-1 s-1 at room temperature is reported. The absorption spectrum of this material covers an electromagnetic spectrum in the infrared regime not served by black phosphorus and is useful for range finding applications as the earth atmosphere has good transparency in this spectral range. Additionally, a low contact resistance of 289 Ω µm is achieved using a nickel phosphide alloy contact with an edge contacted interface via sputtering and thermal treatment.

Structural, optical and dielectric properties of transition metal (MFe2O4; M = Co, Ni and Zn) nanoferrites

Abstract: In the present work, transition metal spinel ferrite (MFe2O4; M = Co, Ni, Zn) nanostructures synthesized by chemical co-precipitation method. XRD analysis confirms the formation of cubic spinel-type structure with space group Fd3m and the average crystallite size calculated by Scherrer's formula found to be in 9–14 nm range. Scanning electron microscopy was used to study surface morphology of the samples. Moreover, Raman and PL spectra also confirm the formation of the cubic structure. The Raman spectra measured on cobalt, nickel and zinc ferrite revealed a larger number of phonon bands than expected for the cubic spinel structure. The calculated optical energy band gaps, obtained by Tauc's relation from UV–Vis absorption spectra are found to be as 2.44, 3.54 and 3.25 eV for CoFe2O4, NiFe2O4&ZnFe2O, respectively. The analysis of the complex impedance spectra of all ferrites samples shows the presence of one semicircular arc at all selected temperatures, signifying a key role of the grain boundary contribution. The dielectric constants ( e ′ ) were measured in the frequency range from 10 Hz to 5 MHz at different temperatures and is found to be decreased suddenly with an increase in frequency and maintain a steady state or constant at higher frequencies for all the three samples. The AC conductivity is found to be increased with frequency and temperature of all the three samples which is explained on the basis of Koop's phenomenological theory.

Pressure-Induced Metallization of the Halide Perovskite (CH3NH3)PbI3

Abstract: We report the metallization of the hybrid perovskite semiconductor (MA)PbI3 (MA = CH3NH3+) with no apparent structural transition. We tracked its bandgap evolution during compression in diamond-anvil cells using absorption spectroscopy and observed strong absorption over both visible and IR wavelengths at pressures above ca. 56 GPa, suggesting the imminent closure of its optical bandgap. The metallic character of (MA)PbI3 above 60 GPa was confirmed using both IR reflectivity and variable-temperature dc conductivity measurements. The impressive semiconductor properties of halide perovskites have recently been exploited in a multitude of optoelectronic applications. Meanwhile, the study of metallic properties in oxide perovskites has revealed diverse electronic phenomena. Importantly, the mild synthetic routes to halide perovskites and the templating effects of the organic cations allow for fine structural control of the inorganic lattice. Pressure-induced closure of the 1.6 eV bandgap in (MA)PbI3 demonstra...

Polarizability, optical basicity and electric susceptibility of Er 3+ doped silicate borotellurite glasses

Abstract: Glasses system was fabricated using the chemical composition {[(TeO 2 ) 0.7 (B 2 O 3 ) 0.3 ] 0.8 (SiO 2 ) 0.2 } 1 − x (Er 2 O 3 ) x with x = 0.01, 0.02, 0.03, 0.04 and 0.05 by melt-quenching method. The glasses were subjected to FTIR and XRD to study the glass structural changes and amorphous nature respectively. The absorption spectrum of the glasses were obtained from UV–Vis spectroscopy and used to calculate the energy band gap. Using the Archimedes principle, the density and the molar volume were determined. From the density, molar volume, and energy band gap, other parameters such as refractive index, molar refractive index, metallization criterion, reflection loss, transmission coefficient, polarizability, optical basicity, polaron radius, dielectric constant, optical dielectric constant, electric susceptibility, average electronegativity and others parameters were obtained by calculation. The polarizability values and the optical basicity were found to increase with Er 3 + ions concentration increase. The dielectric constant, optical dielectric constant and the linear electric susceptibility decreased with increase in Er 3 + ions concentration. The properties studied for the erbium doped glass system suggest the glass system has a potential in the EDFA application.

Green synthesis of ZnO nanoparticles by using Calotropis procera leaves for the photodegradation of methyl orange

Abstract: A facile, innovative and inexpensive green route has been demonstrated for the formation of ZnO nanoparticles by biogenic method using aqueous leaf extract of Calotropis procera which acts as a reducing and stabilizing agent. The as prepared ZnO nanoparticles were characterized by a host of different techniques such as X-ray diffraction (XRD), diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM) and fourier transform infrared spectroscopy (FT-IR). The XRD pattern confesses that ZnO nanoparticles associate to hexagonal wurtzite structure. The DRS absorption spectrum shows an absorption edge at 397 nm corresponds to the ground excitonic peak of ZnO nanoparticles and the band gap is found to be 3.1 eV. The FT-IR spectra indicate the presence of hydroxyl groups, aldehydes, amines, ketones, and carboxylic acids which are responsible for biochemical reaction. TEM images shows that the particles of ZnO have spherical shape with size ranging from 15 to 25 nm. ZnO nanoparticles were subjected to photocatalytic application for the degradation of methyl orange under UV light. The photodegradation efficiency of MO was found to be 81% within 100 min under UV light, such an excellent activity is obtained by biogenic ZnO NPs.

Near UV-Visible electronic absorption originating from charged amino acids in a monomeric protein

Abstract: Electronic absorption spectra of proteins are primarily characterized over the ultraviolet region (185–320 nm) of the electromagnetic spectrum. While recent studies on peptide aggregates have revealed absorption beyond 350 nm, monomeric proteins lacking aromatic amino acids, disulphide bonds, and active site prosthetic groups are expected to remain optically silent beyond 250 nm. Here, in a joint theoretical and experimental investigation, we report the distinctive UV-Vis absorption spectrum between 250 nm [e = 7338 M−1 cm−1] and 800 nm [e = 501 M−1 cm−1] in a synthetic 67 residue protein (α3C), in monomeric form, devoid of aromatic amino acids. Systematic control studies with high concentration non-aromatic amino acid solutions revealed significant absorption beyond 250 nm for charged amino acids which constitute over 50% of the sequence composition in α3C. Classical atomistic molecular dynamics (MD) simulations of α3C reveal dynamic interactions between multiple charged sidechains of Lys and Glu residues present in α3C. Time-dependent density functional theory calculations on charged amino acid residues sampled from the MD trajectories of α3C reveal that the distinctive absorption features of α3C may arise from two different types of charge transfer (CT) transitions involving spatially proximal Lys/Glu amino acids. Specifically, we show that the charged amino (NH3+)/carboxylate (COO−) groups of Lys/Glu sidechains act as electronic charge acceptors/donors for photoinduced electron transfer either from/to the polypeptide backbone or to each other. Further, the sensitivity of the CT spectra to close/far/intermediate range of encounters between sidechains of Lys/Glu owing to the three dimensional protein fold can create the long tail in the α3C absorption profile between 300 and 800 nm. Finally, we experimentally demonstrate the sensitivity of α3C absorption spectrum to temperature and pH-induced changes in protein structure. Taken together, our investigation significantly expands the pool of spectroscopically active biomolecular chromophores and adds an optical 250–800 nm spectral window, which we term ProCharTS (Protein Charge Transfer Spectra), for label free probes of biomolecular structure and dynamics.

Tracking the insulator-to-metal phase transition in VO2 with few-femtosecond extreme UV transient absorption spectroscopy.

Abstract: Coulomb correlations can manifest in exotic properties in solids, but how these properties can be accessed and ultimately manipulated in real time is not well understood. The insulator-to-metal phase transition in vanadium dioxide (VO2) is a canonical example of such correlations. Here, few-femtosecond extreme UV transient absorption spectroscopy (FXTAS) at the vanadium M2,3 edge is used to track the insulator-to-metal phase transition in VO2 This technique allows observation of the bulk material in real time, follows the photoexcitation process in both the insulating and metallic phases, probes the subsequent relaxation in the metallic phase, and measures the phase-transition dynamics in the insulating phase. An understanding of the VO2 absorption spectrum in the extreme UV is developed using atomic cluster model calculations, revealing V3+/d2 character of the vanadium center. We find that the insulator-to-metal phase transition occurs on a timescale of 26 ± 6 fs and leaves the system in a long-lived excited state of the metallic phase, driven by a change in orbital occupation. Potential interpretations based on electronic screening effects and lattice dynamics are discussed. A Mott-Hubbard-type mechanism is favored, as the observed timescales and d2 nature of the vanadium metal centers are inconsistent with a Peierls driving force. The findings provide a combined experimental and theoretical roadmap for using time-resolved extreme UV spectroscopy to investigate nonequilibrium dynamics in strongly correlated materials.