Transient absorption induced by a picosecond electron pulse in the fused silica windows of an optical cell

The transient absorption induced by picosecond pulse radiolysis in the windows of a fused silica optical cell is investigated with pump probe techniques in the UV and the visible range. After excitation with an electron pulse of 7 MeV and an effective duration of around 10 ps the absorbance changes during relaxation are recorded up to nanoseconds with a supercontinuum and a single wavelength probe at 263 nm. The complex spectral signatures and kinetics of the empty cell are set into relation with the transient absorption of water radiolysis. Special care is taken to assure equal irradiation conditions for the comparative measurements over the large spectral range. The results reveal clearly that the transient absorption induced in the fused silica cell is not negligible. The transient signals due to the cell should be considered in picosecond pulse radiolysis of solutions in order to avoid important errors on the time dependent yield of transient species, particularly of those absorbing in the UV.     

In situ femtosecond spectroelectrochemistry of Au(1 1 1) in an aqueous chloride solution

In this paper we report the first in situ femtosecond spectroelectrochemistry experiment employing a broadband probe, allowing the measurement of ultrafast transient visible spectra with a fixed pump wavelength. We investigated in situ femtosecond transient reflectivity of a Au(1 1 1) electrode in contact with an aqueous KCl solution. The pump wavelength was set at 780 nm and a supercontinuum probe was employed, yielding ultrafast spectral information on the electron thermalisation dynamics in the range 450–650 nm. Electrochemical control allowed to investigate the dynamic response to different Cl^? adsorption conditions.     

Synthesis of ZnS nanoparticles from pyridine adducts of zinc(II) dithiocarbamates

Zn(thqdtc)₂, Zn(thqdtc)₂(py) and Zn(thiqdtc)₂(py) (where thqdtc = 1,2,3,4-tetrahydroquinolinecarbodithioate, thiqdtc = 1,2,3,4-tetrahydroisoquinolinecarbodithioate and py = pyridine) have been used as single source precursors for the synthesis of ZnS nanoparticles. The formation of ZnS nanoparticles was achieved by thermal decomposition of the complex under heating in presence of triethylenetetraamine. Transmission electron microscopy, energy dispersive X-ray analysis (EDAX) and powder X-ray diffraction studies were carried out to study the structure and morphology of the nanoparticles. The optical properties of the ZnS nanoparticles were studied by UV–visible and fluorescence emission spectral studies. UV–visible absorption spectral studies indicate a blue shift in the absorption maxima due to the quantum size effect. A single crystal X-ray analysis was carried out for a precursor [Zn(thqdtc)₂].     

Time-resolved spectroscopy at the picosecond laser-triggered electron accelerator ELYSE

ELYSE is a fast kinetics center created for pulse radiolysis with picosecond time-resolution. The facility is a 4–9 MeV electron accelerator using a subpicosecond laser pulse to produce an electron pulse from a Cs₂Te semiconductor photocathode and RF gun technology for the electron acceleration. The pulse duration is around 5 ps at low charge (<2 nC) and high energy (9 MeV), and is under routine conditions 10 ps at higher charge (5 nC) and >8 MeV. The dark current at the target is less than 1% of the pulse photocurrent.Time-resolved absorbance measurements in cells placed in front of the electron beam are achieved using pulsed laser diodes, or a xenon flash lamp as light sources, and photodiodes connected to a 3 GHz transient digitizer or a streak camera (250–800 nm range and 3.7 ps time resolution) as detection instruments. In addition, the synchronization between the laser beam and the electron beam is exploited to measure the absorbance by a pump-probe set-up, the pump being the electron pulse produced by the laser pulse, and the probe being part of the laser beam (120 fs–3 ps) delayed by a variable optical line.     

Preparation and optical absorption of electrodeposited or sputtered,dense or porous nanocrystalline CuInS2 thin films

Copper indium disulphide thin films were obtained by one-step deposition with two different techniques. Films are synthesised by electrodeposition using a single electrolytic bath and by r.f. sputtering using a single target. Deposition rates were about 75 nm/min and 2.5–6.5 nm/min, respectively. Electrodeposited films have rough and porous surfaces, with no preferential orientation. Smooth or particle-covered surfaces were observed for sputtered films with a highly (112)-oriented chalcopyrite structure. Absorption coefficients calculated from transmittance spectra have high values in visible range. Electrodeposited samples present higher absorption coefficients on a larger wavelength range. A relationship between morphology and optical properties was found; absorption coefficients increase with porosity and roughness of the films. Band gap values of about 1.3 eV for electrodeposited and 1.5 eV for sputtered thin films were calculated.     

Substitution reactions of thorium(IV) acetate to synthesize nano-sized carboxylate complexes

Some mixed-ligand thorium(IV) complexes with the general formula [Th(OOCCH₃)_4?nL_n] (L = anions of myristic, palmitic or stearic acid and n = 1–4) have been synthesized by the stepwise substitution of acetate ions of thorium(IV) acetate with straight chain carboxylic acids in toluene under reflux. The complexes were characterized by elemental analyses, spectral (electronic, infrared, NMR and powder XRD) studies, electrical conductance and magnetic susceptibility measurements. Doubly and triply bridged coordination modes of the ligands were established by their infrared spectra and nano-size of the complexes by powder XRD. Room temperature magnetic susceptibility measurements revealed diamagnetic nature of the complexes. Electronic absorption spectra of the complexes showed π → π*, n → π* and charge transfer transitions. Molar conductance values indicated the complex to be non-electrolytes. These are a new type of mixed-ligand thorium(IV) complexes for which a nano-sized, oxygen bridged polymeric structure has been established on the basis of physico-chemical studies.     

Ag2S quantum dot-sensitized solar cells

We present a new photosensitizer – Ag₂S quantum dots (QDs) – for solar cells. The QDs were grown by the successive ionic layer adsorption and reaction deposition method. The assembled Ag₂S-QD solar cells yield a best power conversion efficiency of 1.70% and a short-circuit current of 1.54 mA/cm² under 10.8% sun. The solar cells have a maximal external quantum efficiency (EQE) of 50% at λ = 530 nm and an average EQE of ～ 42% over the spectral range of 400–1000 nm. The effective photovoltaic range covers the visible and near-infrared spectral regions and is ～ 2–4 times broader than that of the cadmium chalcogenide systems — CdS and CdSe. The results show that Ag₂S QDs can be used as a highly efficient and broadband sensitizer for solar cells.     

Gamma ray induced changes on vibrational spectroscopic properties of strontium alumino-borosilicate glasses

The present investigation reports the effect of influence of aluminum ions on radiation damage of strontium borosilicate glasses studied by means of spectroscopic (viz., optical absorption (OA), infrared and Raman spectra). The composition of the glasses chosen for the study is 40SrO–xAl₂O₃–(15-x) B₂O₃–40SiO₂ (x = 5, 7.5, 10), all in mol%. The glasses were synthesized by conventional melt quenching method. Later, the samples were exposed to gamma (γ) radiation dose of strengths 10 kGy and 30 kGy with a dose rate of 1.5 Gy/s using ⁶⁰Co as radiation source. The infrared spectra (IR), Raman spectra and optical absorption (OA) spectra of the samples were recorded at ambient temperature before and after irradiation. The OA spectra of the pre-irradiated samples do not exhibit any absorption bands in the UV–vis regions and IR and Raman spectra exhibited conventional vibrational bands due to different borate, silicate AlO₄ and AlO₆ structural units. The OA spectra of post irradiated samples exhibited a broad absorption band in the wavelength region 600–750 nm; it is attributed to electron trapped color centers. The intensity of this peak is observed to increase with increase of the γ-ray dose. Considerable changes in the intensities of various bands in the IR and Raman spectra were also observed. The changes were explained based on structural modifications taking place in the glass network due to γ-ray irradiation and finally it is concluded that the glasses mixed with 10.0 mol% of Al₂O₃ are relatively more radiation resistant.     

Spectral broadening in quantum dots-sensitized photoelectrochemical solar cells based on CdSe and Mg-doped CdSe nanocrystals

In order to absorb a broad spectrum in visible region, a co-sensitized TiO₂ electrode was prepared by CdSe and Mg-doped CdSe quantum dots (Q dots). The power conversion efficiency of the co-sensitized Q dots photoelectrochemical solar cells (PECs) showed 1.03% under air mass 1.5 condition (I = 100 mW/cm²), which is higher than that of individual Q dots-sensitized PECs. The incident-photon-to-current conversion efficiency of the co-sensitized PECs showed absorption peaks at 541 and 578 nm corresponding to the two Q dots and displayed a broad spectral response over the entire visible spectrum in the 500–600 nm wavelength domains.     

A multimodal spectrometer for Raman scattering and near-infrared absorption measurement

Raman and infrared (IR) spectroscopy are complementary spectroscopic techniques. However, measurement of Raman and IR spectra are commonly carried out on separate instruments. A dispersive system that enables both Raman spectroscopy and NIR spectroscopy was designed, built, and tested. The prototype system measures spectral ranges of 2600–300 cm⁻¹ and 752–987 nm for Raman and NIR channels, respectively. A wavelength accuracy better than 0.6 nm and spectral resolution better than 1 nm (14.4 cm⁻¹ for Raman channel) could be achieved with our configuration. The linearity of spectral response was better than 99.8%. The intensity stability of the instrument was found to be 0.7% and 0.4% for Raman and NIR channels, respectively. The performance of the instrument was evaluated using binary aqueous solutions of ethanol and ovalbumin. It was found that ethanol concentrations (2–10%) could be predicted with a root mean squared error of prediction (RMSEP) of 0.45% using Raman peak height at 882.2 cm⁻¹. Quantification of ovalbumin concentration (8–16 g/L) in aqueous solutions and in denatured states yielded RMSEP values of 1.05 g/L and 0.74 g/L, respectively. Using concentration as external perturbation in two-dimensional correlation spectroscopy (2DCOS), heterospectral correlation analysis revealed the relationship between NIR and Raman spectra.     

Radiation induced in-situ generation of conductivity in the blends of polyaniline-base with chlorinated-polyisoprene

Radiation induced acid doping of PANI to generate electrical conductivity was achieved by radiation induced HCl release from chlorinated-polyisoprene (ClPIP). Blends of PANI with ClPIP were prepared by mechanical mixing/grinding in the composition range of 9–43% ClPIP by weight and pelletized under 10 t press. The pellets were irradiated in ⁶⁰Co Gammacell in air at room temperature to doses up to 300 kGy. The maximum electrical conductivity increase was observed for the blend PANI43 which changed from 10^?10 to 10^?4 S cm^?1 when it was irradiated to 300 kGy dose. Radiation induced changes on the blends were also studied by UV–vis spectroscopy using reflection technique and FTIR spectroscopy. The broad absorption band in the visible range (630 nm) increased by increasing irradiation dose. The band (1110 cm^?1) in the IR spectra which is indicative of conductivity showed linear correlation with irradiation dose.     

FTIR investigation of spray-dried milk protein concentrate powders

Fourier transform infrared (FTIR) spectroscopy was used to examine the conformation of proteins in spray-dried milk protein concentrate (MPC) powders and to determine if the spectral changes could be related to nitrogen solubility of these powders. MPC samples (83–92% protein, dry basis) were prepared using a range of processing conditions and stored for 4 weeks at 21 °C. FTIR spectra were collected in the mid infrared (MIR) region between 4000 and 600 cm⁻¹. FTIR data was pre-processed to remove physical effects causing discrimination between samples using firstly second derivatives and normalization and secondly the extended multiplicative scatter correction (EMSC) technique. The FTIR spectral changes were subsequently assessed using second derivative spectroscopy and principal components analysis (PCA) in the amide I and II regions (1700–1400 cm⁻¹) and the fingerprint region (1800–700 cm⁻¹). PCA analysis showed that the different powder preparations could be separated on scores plots but the separation was not related to nitrogen solubility per se. However, changes in nitrogen solubility of individual MPC powders during storage could be correlated to changes in FTIR spectra. PCA analysis of FTIR spectra could generally discriminate between MPC powders that had lost significant nitrogen solubility (9–20%) and those in which nitrogen solubility was preserved on storage. There were changes in intensity and/or position of bands at 1630 cm⁻¹ when the solubility of a stored sample decreased substantially. The results of this work also show that EMSC data pre-processing for these samples gives comparable results when compared with more complicated data pre-processing for the removal of physical effects.     

Structures and spectroscopic properties of meso-tetrasubstituted porphyrin complexes: Meso-substitutional and central metallic effect study based on density functional theory calculations

Effects of the meso-substituents and central metals on the molecular structures, atomic charges, molecular orbital energy gaps, electronic absorption spectra, and infrared (IR) spectra of 12 meso-tetrasubstituted porphyrin complexes including metal-free porphyrins H₂P or (Por = TPP, TFPP, TClPP, TPyP) (1–4) and their metal complexes MPor (M = Mg, Zn; Por = TPP, TFPP, TClPP, TPyP) (5–12) [TPP = meso-tetrakis(phenyl)porphyrinate; TFPP = meso-tetrakis(4-fluorophenyl)porphyrinate; TClPP = meso-tetrakis(4-chlorophenyl)porphyrinate; TPyP = meso-tetrakis(4-pyridyl) porphyrinate] are systematically studied by density functional theory calculations at the B3LYP/6-31G(d) level. Good consistency was found between the calculated molecular structures and the experimental X-ray crystallography ones for 1, 3, and 4, and between the simulated electronic absorption and IR spectra and the experimental ones for 1 and 4. The calculation results reveal that introducing substituents at the meso positions of porphyrin induces increasing change in the molecular structures, atomic charges distribution, HOMO and LUMO energy, electronic absorption spectra, and IR spectra along with the increase in the electron-withdrawing ability of substituents in the order of phenyl, 4-fluorophenyl, 4-chlorophenyl, and pyridyl group. Furthermore, the central metal in porphyrins displays much significant influence on the structure and spectroscopic properties of meso-substituted porphyrin complexes. The electronic absorption and IR spectra of 1–12 are compared and assigned in detail. The present work should be not only helpful towards understanding the meso-substitutional and central metallic effects on the structure and spectroscopic properties of meso-substituted porphyrin complexes, but also useful in correctly assigning electronic absorption and IR spectra for porphyrin complexes.     

Growth and characterization of naphthalene single crystals grown by modified vertical Bridgman method

The large size 20 mm diameter naphthalene single crystals were grown by modified vertical Bridgman method. The optical quality of the grown crystal was analyzed by photoluminescence and ultraviolet visible absorption spectral measurements. Photoluminescence spectrum indicated violet emission at 410 nm. The UV–vis absorption spectrum shows the maximum at 219.32 nm. The microhardness measurements and differential thermal analysis performed to analyze the mechanical and thermal stability of the as grown crystals. The dielectric measurements were carried out at five frequencies, viz., 100 Hz, 1 kHz, 10 kHz, 100 kHz and 1 MHz and at various temperatures, ranging from 308 K to 348 K indicate an increase of the dielectric parameters with the increase of temperature at all the five frequencies. The conductivity of the material is understood to be more of electronic in nature. Also, the increase in the dielectric parameters with that of temperature is due to the temperature variation of electronic polarizability.     

Light-induced spin crossover in Fe(II)-based complexes: The full photocycle unraveled by ultrafast optical and X-ray spectroscopies

The light-induced spin and structure changes upon excitation of the singlet metal-to-ligand charge transfer (¹MLCT) state of Fe(II)-polypyridine complexes are investigated in detail in the case of aqueous iron(II)-tris-bipyridine ([Fe^II(bpy)₃]²⁺) by a combination of ultrafast optical and X-ray spectroscopies. Polychromatic femtosecond fluorescence up-conversion, transient absorption studies in the 290–600 nm region and femtosecond X-ray absorption spectroscopy allow us to retrieve the entire photocycle upon excitation of the ¹MLCT state from the singlet low-spin ground state (¹GS) as the following sequence: ^1,3MLCT → ⁵T → ¹GS, which does not involve intermediate singlet and triplet ligand-field states. The population time of the HS state is found to be ～150 fs, leaving it in a vibrationally hot state that relaxes in 2–3 ps, before decaying to the ground state in 650 ps. We also determine the structure of the high-spin quintet excited state by picosecond X-ray absorption spectroscopy at the K-edge of Fe. We argue that given the many common electronic (ordering of electronic states) and structural (Fe–N bond elongation in the high-spin state, Fe–N mode frequencies, etc.) similarities between all Fe(II)-polypyridine complexes, the results on the electronic relaxation processes reported in the case of [Fe^II(bpy)₃]²⁺ are of general validity to the entire family of Fe(II)-polypyridine complexes.     

Ionic transient species in irradiated poly(vinyl chloride) film

The studies of transient species in irradiated poly(vinyl chloride) (PVC) film have been carried out with the main aim of investigating the charge trapping in a pure system. In PVC, pulse radiolysis gives electron-positive hole pairs. The electron can generate a matrix anion due to the presence of chlorine atom in the PVC macromolecules followed by Cl⁻ detachment. The positive hole may be stabilized as a short-lived matrix cation characterized by visible absorption band with wide maximum in the 350–650 nm range. The positive holes can be scavenged by additives like pyrene, Py and respective radical-ions of Py can be detected. The rate of Py radical cations decay at ∼450 nm was found to be temperature dependent. Two linear parts of the Arrhenius plot were observed which intersected in the 200–240 K range, which is close to the mechanical loss peak connected with the β relaxation in PVC matrix. The activation energies calculated for two parts of Arrhenius plot were equal to 0.40 kJ mol⁻¹ for T < 200 K and 52.6 kJ mol⁻¹ for T > 240 K. The novel mechanism of the ionic and radical reactions in PVC is proposed and discussed.     

A facile synthetic strategy for mesoporous crystalline copper–polyaniline composite

A facile and novel strategy for preparing mesoporous crystalline copper–polyaniline composite is reported wherein the reaction is carried out at room temperature using copper nitrate as the oxidizing agent and methanol as the solvent. The composite obtained as a precipitate has been characterized using UV–visible absorption spectroscopy (UV–vis), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption–desorption method, Barrett–Joyner–Halenda (BJH) method, Brunauer–Emmett–Teller method (BET) and thermogravimetric analysis (TGA). The XRD studies in conjunction with the BJH method reveals that the composite has crystalline nature with a mesoporous structure and has a diameter of 3.5 nm. The specific surface area of copper–polyaniline composite is estimated to be as high as 63.2 m² g^?1 using the BET surface area plot. The characterization of the filtrate indicates the presence of pernigraniline with a very small weight percent of copper.     

Visible light photocatalysis by a Titania–Rhodium(III) complex

Titania hybrid photocatalysts containing 0.5, 1.0, 2.0, and 5.0 wt% of rhodium(III) were prepared by chemisorption of RhCl₃ × 3H₂O onto anatase hydrate powder (TH). Analytical data suggest that a titania–trichlororhodate complex is produced containing a [TiO₂]–O–Rh bond.Similar results are found in the case of modification by RhBr₃ × 3H₂O. Diffuse reflectance spectra exhibit an absorption shoulder throughout the visible region down to 700 nm. Photoelectrochemical measurements indicate that the quasi-Fermi level of electrons is gradually shifted to more anodic potentials with increasing rhodium loading reaching a value of ?0.34 V at pH 7 (vs. NHE) in the case of 5.0%RhCl₃/TH. This is more anodic by 210 mV as compared to unmodified TH. Upon visible light irradiation this photocatalyst induces a fast mineralization of 4-chlorophenol whereas cyanuric acid, which is known to be mineralized in the presence of the analogous Pt(IV) modified titania, is not degraded.     

Infrared absorption spectrum of HoFe3(BO3)4 crystal

Infrared (IR) absorption spectra of HoFe₃(BO₃)₄ crystal have been obtained in spectral range 30–7000 cm⁻¹ at temperatures from 4 to 423 K. Vibrational frequencies have been simulated with ‘Lady’ software package both for high-temperature and low-temperature phases. The experimental spectra have been analyzed on the basis of calculated data, and interpreted within the framework of internal vibrations of ionic complexes of HoFe₃(BO₃)₄ crystal lattice. The spectral range under study was observed to have no Davydov splitting of internal vibrational modes due to unit cell multiplication. No effects of magnetic ordering on the IR spectra of the crystal under study were observed in the low-temperature range.     

Biomimetic synthesis of silver nanoparticles by Citrus limon (lemon) aqueous extract and theoretical prediction of particle size

In the present study, silver nanoparticles were rapidly synthesized at room temperature by treating silver ions with the Citrus limon (lemon) extract. The effect of various process parameters like the reductant concentration, mixing ratio of the reactants and the concentration of silver nitrate were studied in detail. In the standardized process, 10^?2 M silver nitrate solution was interacted for 4 h with lemon juice (2% citric acid concentration and 0.5% ascorbic acid concentration) in the ratio of 1:4 (vol:vol). The formation of silver nanoparticles was confirmed by Surface Plasmon Resonance as determined by UV–Visible spectra in the range of 400–500 nm. X-ray diffraction analysis revealed the distinctive facets (1 1 1, 2 0 0, 2 2 0, 2 2 2 and 3 1 1 planes) of silver nanoparticles. We found that citric acid was the principal reducing agent for the nanosynthesis process. FT-IR spectral studies demonstrated citric acid as the probable stabilizing agent. Silver nanoparticles below 50 nm with spherical and spheroidal shape were observed from transmission electron microscopy. The correlation between absorption maxima and particle sizes were derived for different UV–Visible absorption maxima (corresponding to different citric acid concentrations) employing “MiePlot v. 3.4”. The theoretical particle size corresponding to 2% citric acid concentration was compared to those obtained by various experimental techniques like X-ray diffraction analysis, atomic force microscopy, and transmission electron microscopy.