Determination of band gaps of self-assembled carbon nanotube films using Tauc/Davis–Mott model

The band gaps of self-assembled single-walled carbon nanotube (SWNT) films have been determined through curve fitting using the semi-empirical Tauc and Davis–Mott model, based on the measurement of optical absorption at the visible and near infrared range. This study provides a practicable option for the determination of band gaps for ultra-thin SWNT films or multi-walled carbon nanotube films whose vHs peaks cannot be well resolved in absorption spectra.     

Tunable diode laser study of the ν3 band of oxirane

We have measured and fitted over 600 well-resolved lines in the ν₃ ring breathing band of oxirane. The spectrum is accurately reproduced by previously determined rotational and centrifugal distortion constants for the ground state, together with newly determined rotational, quartic and some sextic distortion constants for the upper state. The magnitudes of the distortion constants reveal some evidence of Coriolis interactions with nearby states. The band centre was determined as .     

First-principle study on the electronic structure and the anti-ferromagnetic properties of the organic-inorganic hybrid compound [Co(μ1,3-SCN)2(μ1,6-dmpzdo)]n

The electronic and the magnetic properties of the molecule-based magnet [Co(μ_1,3-SCN)₂(μ_1,6-dmpzdo)]n (where dmpzdo=2,5-dimethylpyrazine-1,4-dioxide) have been investigated using first-principles, namely density-functional theory (DFT) with the generalized gradient approximation (GGA) method and the full-potential linearized augmented plane-wave method (FP_LAPW). The total energy, the spin magnetic moments and the density of states (DOSs) were all calculated and spin distributions in ferromagnetic and anti-ferromagnetic (AFM) states of it have been obtained by the calculation. The electronic structure and magnetic coupling between cobalt ions along chain are discussed, and the calculations reveal that the compound [Co(μ_1,3-SCN)₂(μ_1,6-dmpzdo)]n has a stable anti-ferromagnetic ground state, which is in good agreement with the experimental results.     

Electrical properties and photoconductivity of polyaniline/sulfonated poly(arylene ether sulfone) composite films

Temperature dependent electrical conductivity of the polyaniline-sulfonated poly(arylene ether sulfone) with 35 mol percent sulfonation (PANI-BPS35) composite films were investigated in the temperature range of 80–380 K. These composite films showed semiconductor behavior with the exponential variation of inverse temperature dependence of electrical conductivity. Calculated Mott’s parameters showed that variable range hopping mechanism is the dominant transport mechanism for the carriers in low temperature region. Photoconductivity of the PANI-BPS35 composite films having 10, 20, and 40 weight percent conductive filler under various illumination intensities was also studied. Photocurrent of the composite films increased with increasing both polyaniline weight fraction and temperature. Finally, the effect of doping on both electrical conductivity and the photoconductivity of the composite films was investigated.     

High-resolution study of the ν1/ν5 and 2ν1/ν1+ν5 P-H stretching bands of PH2D

The P-H stretching bands ν₁/ν₅ and 2ν₁/ν₁+ν₅ were recorded using a Bruker 120 HR interferometer with a resolution of 0.0042 and 0.0088 cm⁻¹, respectively, and analyzed. From the fits 33 and 50, respectively, vibrational, rotational, centrifugal distortion, and resonance interaction parameters were obtained. These reproduce 668 and 497 rovibrational energies of the pairs of states ν₁/ν₅ and 2ν₁/ν₁+ν₅ with experimental accuracies, rms=0.00016 and , respectively. “Local mode” behavior of the PH₂ fragment is established and discussed in detail.     

Optical parameters of nanostructured thin films of?electromagnetite Pb1? x Sr x (Fe0.012Ti0.988)O3

Polycrystalline Pb_1−x Sr _x (Fe_0.012Ti_0.988)O₃ (0.2≤x≤0.4) (PSFT) thin films have been grown on fused quartz substrates by metallo-organic decomposition technique. The grown films were characterized using X-ray diffraction (XRD), atomic force microscopy (AFM), source meter and UV–Vis–NIR spectrophotometer to determine the structural, microstructural, dc resistivity and optical properties. The XRD pattern confirmed that the PSFT films has distorted tetragonal single phase, which close to cubic at higher Sr concentration. AFM analysis revealed that the grains size reduces with increasing Sr concentration and their average values lies in the range of 26–9 nm. The higher values of dc resistivity of PSFT nano grains indicate that the transmission of light occurs within these grains up to short wavelength. The refractive index and the extinction coefficient were determined from the optical transmission spectrum in the wavelength range of 200–1100 nm and compared with that theoretically calculated, when fitted to a single oscillator model. The values of optical band gap were determined from Tauc’s extrapolation fitting and suggests that the transformation of electrons during transmission of light through local states within Fermi gap.     

New analysis of the ν5+ν9−ν9 hot band of HNO3

Nitric acid which is an important NO_x atmospheric reservoir molecule exhibits a strong absorption in the spectral region. Since this region, which corresponds to an atmospheric window, is one of the most commonly used for the retrieval of HNO₃ in the atmosphere it is essential to have the best possible corresponding spectral parameters. Updates of these spectral line parameters were recently performed in the last versions of the atmospheric databases. They concern the line positions and intensities not only of the two interfering cold bands ν₅ and 2ν₉ but also of the ν₅+ν₉−ν₉ hot band. This hot band exhibits indeed a sharp and strong Q branch at which is clearly observable in atmospheric spectra and is used for the retrievals. However, in spite of these recent updates, it proved that the spectral parameters of the hot band are not accurate enough to reproduce accurately the observed atmospheric HNO₃ absorption in ATMOS spectra. The present paper is dedicated to a more accurate analysis of this hot band using new laboratory high-resolution (0.002-) Fourier transform spectra. As a consequence, new and more precise line positions and line intensities (about 35% weaker than in HITRAN2K) were derived leading to a significant improvement in the simulation of atmospheric spectra.     

High-resolution infrared and theoretical study of the fundamental bands ν6, ν7, ν9 and ν13 of 1,2,3-thiadiazole

The Fourier transform gas-phase IR spectrum of 1,2,3-thiadiazole, C₂H₂N₂S, has been recorded with a resolution of ca. 0.003 cm⁻¹ in the 700-1100 cm⁻¹ spectral region. Four fundamental bands ν₆(A^/; 1101.8 cm⁻¹), ν₇(A^/; 1038.8 cm⁻¹), ν₉(A^/, 858.9 cm⁻¹), and ν₁₃(A^//; 746.2 cm⁻¹) have been analyzed using the Watson model in A-reduction. Two additional bands, ν₈ (A^/; 894.6 cm⁻¹) and ν₁₂(A^//; 881.2 cm⁻¹) were assigned by their weak Q-branches. Ground state rotational and quartic centrifugal distortion constants as well as upper state spectroscopic constants have been obtained from fits. A number of weak global and local interactions are present in the bands. The resonances identified were qualitatively explained by Coriolis type perturbations with neighboring levels. Ground state rotational and quartic centrifugal distortion constants, anharmonic frequencies, and vibration-rotational α-constants predicted by quantum chemical calculations using a cc-pVTZ basis and B3LYP methodology, have been compared with the present experimental data, where there is generally good agreement.     

High resolution analysis of the ν7 and ν9 bands of DCOOH

The 7¹ and 9¹ vibrational states of deuterated species of formic acid molecule DCOOH have been recorded by a FTIR spectrometer in the region 450- at a resolution of and a millimeter wave spectrometer. In the analysis microwave transitions from literature were used in addition to 14 835 assigned IR and 114 millimeter wave lines in the 7¹ and 9¹ vibrational states. The analysis resulted in band origins, rotational, centrifugal distortion, and eight interaction parameters of the Coriolis coupled 7¹ and 9¹ vibrational states. RMS deviation of the fit was for the IR data and the maximum values of J and K_a quantum numbers in the fit were 64, 28 and 64, 30 for 7¹ and 9¹ states, respectively.     

High-resolution infrared and theoretical study of the fundamental bands ν2, ν4 and ν9 and the c-Coriolis interacting dyad ν5, ν14 of 1,3,4-thiadiazole

The Fourier transform gas-phase IR spectrum of 1,3,4-thiadiazole, C₂H₂N₂S, has been recorded with a resolution of ca. 0.003 cm⁻¹ in the 800-1500 cm⁻¹ spectral region. Five fundamental bands ν₂(A₁; 1391.9 cm⁻¹), ν₄(A₁; 964.4 cm⁻¹), ν₅(A₁; 894.6 cm⁻¹), ν₉(B₁; 821.5 cm⁻¹), and ν₁₄(B₂; 898.4 cm⁻¹) have been analysed using the Watson model. Ground state rotational and quartic centrifugal distortion constants as well as upper state spectroscopic constants have been obtained from fits. The ν₄ and ν₉ bands are unperturbed while a strong c-Coriolis resonance perturbs the close-lying ν₅ and ν₁₄ bands. This dyad system has been analysed by a model including first and second order c-Coriolis resonance using the theoretically predicted Coriolis coupling constant . The ν₂ band is strongly perturbed by a local resonance, and we obtain a set of spectroscopic parameters using a model including second order a-Coriolis resonance with the inactive ν₁₀ + ν₁₄ band. Ground state rotational and quartic centrifugal distortion constants, anharmonic frequencies, and vibration-rotational α-constants predicted by quantum chemical calculations using a cc-pVTZ basis and B3LYP methodology, have been compared with the present experimental data, where there is generally good agreement.     

Preparation and characterization of biodegradable poly(ε-caprolactone)-based gel polymer electrolyte films

Biodegradable polymer electrolyte films based on poly(ε-caprolactone) (PCL) in conjunction with lithium tetrafluoroborate (LiBF₄) salt and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIMBF₄) ionic liquid were prepared by solution cast technique. The structural, morphological, thermal, and electrical properties of these films were examined using X-ray diffraction (XRD), optical microscopy (OM), differential scanning calorimetry (DSC), and impedance spectroscopy. The XRD and OM results reveal that the pure PCL possesses a semi-crystalline nature and its degree of crystallinity decreases with the addition of LiBF₄ salt and EMIMBF₄ ionic liquid. DSC analysis indicates that the melting temperature and enthalpy are apparently lower for the 40 wt% EMIMBF₄ gel polymer electrolyte as compared with the others. The ambient temperature electrical conductivity increases with increasing EMIMBF₄ concentration and reaches a high value of ～2.83?×?10^?4 S cm^?1 for the 85 PCL:15 LiBF₄ + 40 wt% EMIMBF₄ gel polymer electrolyte. The dielectric constant and ionic conductivity follow the same trend with increasing EMIMBF₄ concentration. The dominant conducting species in the 40 wt% EMIMBF₄ gel polymer electrolyte determined by Wagner’s polarization technique are ions. The ionic conductivity of this polymer electrolyte (～2.83?×?10^?4 S cm^?1) should be high enough for practical applications.     

Simultaneous analysis of the 2ν2, 2ν5, and ν2 + ν5 vibration-rotation bands of CH3Br

Previous studies of the parallel bands 2ν₂ and $\text{2ν}{}_5{}^0$ of CH₃Br by the two first authors have been completed by the analysis of the weaker perpendicular band ν₂ + ν₅, centered near 2745 cm^?1. It is well known that the v₂ = 1 and v₅ = 1 states of methylbromide are linked by an x-y-type Coriolis interaction. Therefore, in the 2500–2900-cm^?1 range, the levels

$\text{(v}{}_2\text{=2), (v}{}_5\text{2, l}{}_5\text{=0), (v}{}_5\text{=2, l}{}_5\text{±2), (v}{}_5\text{=v}{}_2\text{=1, l=5±1)}$

are linked by a similar interaction. Least-squares and prediction programs have been written to treat this kind of problems and they have been satisfactorily applied to both isotopic species, CH₃⁷⁹Br and CH₃⁸¹Br. A localized resonance in the K = 0 subband of ν₂ + ν₅ has been shown to be due to the 3ν₃ + ν₆ band. No evidence for a strong Fermi resonance between ν₁ and $\text{2ν}{}_5{}^0$ has been found.     

Measurement of the branching ratios for the decays J/ψ → ϱπ and J/ψ → γη′

Decays of the J/ψ (3.1) resonance into final states with two charged hadrons and two photons are investigated. Branching ratios for the decays J/ψ → ?π and J/ψ → γη′ are determined to be

$\text{Г(J/ψ → pφ)}\text{Г(J/ψ → all)}\text{= (1.0± 0.2) ·10}{}^{\mathrm{?2}}\text{,}\text{Г(J/ψ → γη′)}\text{ГJ/ψ → all)}\text{= (2.0± 0.7) ·}{}^{\mathrm{?3}}$

Upper limits for the same decay modes of ψ′ (3.7) are also determined.     

Preparation of poly (styrene)-b-poly (acrylic acid)/γ-Fe2O3 composites

The use of a block copolymer, poly (styrene)-b-poly (acrylic acid) (PS-b-PAA) to prepare a magnetic nanocomposite was investigated. Poly (styrene)-poly (t-butyl acrylate) block copolymer, being synthesized by atom transfer radical polymerization, was hydrolyzed with hydrochloric acid for obtaining PS-b-PAA. The obtained PS-b-PAA was then compounded with the modified γ-Fe₂O₃, and subsequently the magnetic nanocomposite was achieved. The products were characterized by ¹H NMR, FTIR, gel permeation chromatography, thermogravimetric analysis, transmission electron microscopy and vibrating sample magnetometer. The results showed that the nanocomposites exhibited soft magnetism, with the mean diameter of 100 nm approximately.     

Effect of the ceramic grain size and concentration on?the?dynamical mechanical and dielectric behavior of?poly(vinilidene fluoride) Pb(Zr0.53Ti0.47)O3 composites

In this work, poly(vinilidene fluoride)/Pb(Zr_0.53Ti_0.47)O₃([PVDF]_1−x /[PZT] _x ) composites of volumetric fractions x and (0–3) type connectivity were prepared in the form of thin films. PZT powder of crystallite size of 0.84, 1.68, and 2.35 μm in different amounts of PZT (10, 20, 30, and 40%) was mixed with the polymeric matrix. The crystalline phase of the polymeric matrix was the nonpolar α-phase and the polar β-phase. Dielectric and dynamic mechanical (DMA) measurements were performed to these composites in order to evaluate the influence of particle size and the amount of PZT filler with respect to the PVDF matrix. The inclusion of ceramic particles in the PVDF polymer matrix increases the complex dielectric constant and dynamical mechanical response of the composites. A similar behavior is observed for the α- or β-phase of the polymeric matrix indicating that the PVDF polymer matrix is not particularly relevant for the composite behavior. On the other hand, ceramic size and especially content play the major role in the increase of the dielectric response and the room temperature storage modulus. In particular, the storage modulus increases with increasing PZT concentration, but this increase is more pronounced, in terms of maximum value, for the sample with 2.35 μm particle size; DMA reveals two main relaxations in the analyzed samples. A low-temperature process maximum at ca. −40°C, usually labeled by β or α _a associated to the T _g of the polymer and the α-relaxation at temperatures above 30°C. The β-relaxation is also observed in the dielectric measurements. The models used to asses the dielectric behavior of the samples with increasing PZT concentration indicate that the particle–matrix interaction plays a relevant role, as well as the particle asymmetry and relative orientation, being the Yamada model the most appropriate to describe the composite behavior. An erratum to this article can be found at     

High-resolution infrared spectroscopy of the interacting ν9, ν5 + ν6 and 3ν6 levels of CH2BrF

The high-resolution (0.0030 cm⁻¹) Fourier transform infrared spectrum of CH₂⁷⁹BrF has been studied in part of the atmospheric window between 910 and 980 cm⁻¹, the region of the ν₉ (935.847 cm⁻¹) and ν₅ + ν₆ (961.239 cm⁻¹) bands. The ν₉ fundamental consists of a pseudo a-type band induced by Coriolis coupling with ν₅ + ν₆, in turn exhibiting a predominant a-type structure. Several interactions connecting these levels and the dark state 3ν₆ have been assessed. The whole data set is treated using Watson’s A-reduced Hamiltonian in the I^r representation implemented with first order a- and b- and c-type Coriolis terms. A detailed analysis of the rotational structure yields a set of accurate upper-state parameters up to quartic distortion terms for ν₉ and ν₅ + ν₆. In addition, spectroscopic information about the dark ternary overtone of ν₆ has been obtained.     

Effect of Cd and Pb impurities on the optical properties of?fresh?evaporated amorphous (As2Se3)90Ge10 thin films

Transmission spectra (400–1500 nm) of thermally evaporated amorphous [(As₂Se₃)₉₀Ge₁₀]₉₅M₅ thin films have been analyzed to study the effect of impurities (M = Cd and Pb) on their optical properties. The refractive index increases with addition of metal impurities. The dispersion of refractive index has been studied using Wemple–DiDomenico single oscillator model. The optical gap has been estimated using Tauc’s extrapolation and was found to decrease with the addition of metal impurities from 1.46 to 1.36 eV (Cd) and 1.41 eV (Pb) with an uncertainty of ±0.01 eV. The change in optical properties with metal impurities has been explained on the basis of density, polarizability and bond energy of the system.