High resolution infrared spectroscopy of [1.1.1]propellane: The region of the ν9 band

The region of the infrared-active band of the ν₉ CH₂ bending mode [1.1.1]propellane has been recorded at a resolution (0.0025 cm⁻¹) sufficient to distinguish individual rovibrational lines. This region includes the partially overlapping bands ν₉ (e′) = 1459 cm⁻¹, 2ν₁₈ (l = 2, E′) = 1430 cm⁻¹, ν₆ + ν₁₂ (E′) = 1489 cm⁻¹, and ν₄ + ν₁₅ (A₂″) = 1518 cm⁻¹. In addition, the difference band ν₄ − ν₁₅ (A₂″) was observed in the far infrared near 295 cm⁻¹ and analyzed to give good constants for the upper ν₄ levels. The close proximities of the four bands in the ν₉ region suggest that Coriolis and Fermi resonance couplings could be significant and theoretical band parameters obtained from Gaussian ab initio calculations were helpful in guiding the band analyses. The analyses of all four bands were accomplished, based on our earlier report of ground state constants determined from combination differences involving more than 4000 pairs of transitions from five fundamental and four combination bands. This paper presents the analyses and the determination of the upper state constants of all four bands in the region of the ν₉ band. Complications were most evident in the 2ν₁₈ (l = 2, E′) band, which showed significant perturbations due to mixing with the nearby 2ν₁₈ (l = 0, A₁′) and ν₄ + ν₁₂ (E′) levels which are either infrared inactive as transitions from the ground state, or, in the latter case, too weak to observe. These complications are discussed and a comparison of all molecular constants with those available from the ab initio calculations at the anharmonic level is presented.     

Local vibration assisted molecular configurations in poly(vinylidene fluoride) of ordered ferroelectric phase in N,N-dimethylformamide

Amide-based polymer liquids are important for developing biological and optical colloids or nanofluids. Functionalized properties arise from specific molecular structures. In this investigation, we report model molecular configurations of a polymer liquid, 0.3 g/L poly(vinylidene fluoride) (PVF₂) dissolved in liquid N,N-dimethylformamide (DMF), based on the characteristic IR vibration bands. Peculiarly, a ferroelectric β-PVF₂ phase reorders on a linear configuration in support with the DMF molecules, showing a characteristic band 840 cm^− 1 (CH₂ rocking and CF₂ asymmetric stretching) with the trans band at 1275 cm^− 1. Four CO stretching bands ν₁⁰, ν₁¹, ν₁², and ν₁³ of 1650, 1675, 1725, and 1760 cm^− 1 (bandwidth Δν_½ = 180 cm^− 1 in the four bands) arise in four major configurations of DMF-PVF₂ pairs (or derivatives). Only one prominent ν₁⁰ band 1660 cm^− 1 (Δν_½ = 75 cm^− 1) incurs with a shoulder ν₁¹ of 1725 cm^− 1 (Δν_½ = 25 cm^− 1) in two DMF configurations. A ferroelectric field cased in presence of β-PVF₂ leads to enhance IR absorption by as much as an order of magnitude. It leads to converging non-bonding electron density on the amide moiety.     

Effect of La substitution on conductivity and dielectric properties of Bi1−xLaxFeO3 ceramics: An impedance spectroscopy analysis

Bismuth ferrite (BFO) and La-substituted BFO with composition Bi_1−xLa_xFeO₃ (x=0.05, 0.1 and 0.15) (BLFO_x=0.05-0.15) ceramics were prepared using the solid state reaction route. A structural phase transition from rhombohedral phase to triclinic phase was observed for BLFO_x=0.05-0.15 ceramics. Modulus spectroscopy reveals the deviation of dielectric behavior from ideal Debye characteristics and the dependence of conductivity on ion hopping in BFO and BLFO_x=0.05-0.15 ceramics. The conductivity of the BFO ceramics decreases for La content of 5 mol%, followed by a subsequent increase with 10 and 15 mol% of lanthanum doping. The typical values of the activation energies at high temperature reveal the contribution of short range movement of doubly ionized oxygen vacancies to the conduction process in BFO and BLFO_x=0.05 ceramics. Both short range and long range motion of oxygen vacancies are responsible for large conductivity in BLFO_{x=0.1 and 0.15} ceramics.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

The first high-resolution analysis of the 10-μm absorption of thioformaldehyde

The 10 μm region of thioformaldehyde (H₂CS) has been recorded at high resolution (0.005 cm⁻¹) using a Fourier transform spectrometer. H₂CS was produced by low-pressure pyrolysis of a gas flow of C₃H₅SCH₃ in Ar at 560 °C or CH₃SCl at 1150 °C, which was introduced into a multipass White cell with an optical path length of 32 m. Forty scans were recorded for the range 750-1400 cm⁻¹ at a total pressure of 0.15 mbar. A thorough analysis of the three lowest wavenumber fundamental bands, ν₃, ν₄ and ν₆, which fall in this region, has been carried out using a Hamiltonian model, which takes explicitly into account the numerous resonances affecting the ro-vibrational energy levels; especially the massive A-type Coriolis resonance between the out-of-plane wagging mode, ν₄, and the in-plane rocking mode, ν₆. These two modes are only separated by 0.83 cm⁻¹, and they are thoroughly mixed. From the fittings, the following band centers were derived: ν_o (ν₄)=990.18213(40) cm⁻¹, ν_o (ν₆)=991.02021(50) cm⁻¹ and ν_o (ν₃)=1059.20476 (30) cm⁻¹ where the uncertainties are one standard deviation. In addition, a number of relative line intensities were measured permitting the determination of relative values of the first-order transition moments and therefore relative band intensities for all three bands. Finally, a comprehensive list of line wavenumbers and relative intensities has been generated.     

High-Resolution Infrared Studies of ν1, 2ν1, and 2ν4 Bands of CHCl3

The C-H stretching fundamental band ν₁ (3033 cm⁻¹) of chloroform CH³⁵Cl₃ has been investigated together with the first overtone 2ν₁ (5941 cm⁻¹) in order to determine the rotation vibration parameters. From the ν₁ band α₁^C=−0.025 46(41)×10⁻³ cm⁻¹ and α₁^B=−0.010 688(44)×10⁻³ cm⁻¹ were obtained. The hot bands connected to the low lying fundamentals ν₃ and ν₆ have been analyzed and anharmonicity constants have been derived. Both the parallel and the perpendicular component band of the C-H bending overtone 2ν₄ have also been studied. In the parallel band (2410 cm⁻¹) more than 900 lines were included in the fit. In the perpendicular band (2443 cm⁻¹) 2615 lines were fitted using a model with one resonance. Among other things the results C₀−C_v=0.025 262 (20)×10⁻³ cm⁻¹, B₀−B_v=0.134 883 (25)×10⁻³ cm⁻¹, and (Cζ)_v=−0.111 867 56 (30) cm⁻¹ were obtained.     

Magnetostriction of TbxHo0.75−xPr0.25(Fe0.9B0.1)2 (x=0–0.3) compounds

The Tb_xHo_0.75−xPr_0.25(Fe_0.9B_0.1)₂ (x=0, 0.1, 0.15, 0.2, 0.25, and 0.3) compounds are found to stabilize in a cubic Laves phase structure. The lattice parameter, magnetostriction (at 10 kOe), and Curie temperature are found to increase with increasing Tb content. The compound with x=0.15 exhibits a possible anisotropy compensation between the Tb and (Ho/Pr) sublattices. The easy magnetization direction rotates towards the 〈1 1 1〉 from the 〈1 0 0〉 direction, with increasing Tb content. The splitting of the (4 4 0) peak accompanied by the spontaneous magnetostriction-induced rhombohedral distortion is observed for compounds with x?0.15 and the spontaneous magnetostriction (λ_1 1 1) is found to increase with Tb content.     

The first high-resolution analysis of the low-lying ν9 band of propane

The ν₉ fundamental band (C-C-C deformation) of propane (C₃H₈) at 369 cm⁻¹ has been studied at high-resolution (0.0011 cm⁻¹) with spectra recorded using the synchrotron radiation from the French light source facility at SOLEIL coupled to a Bruker IFS 125HR Fourier transform spectrometer. A 2.526 m base multipass cell with optical paths from 10.296 to 151.78 m was used. In addition, a spectrum was also recorded using a conventional globar source. Comparison of these experimental spectra shows clearly the gain obtained on the signal-to-noise ratios with the synchrotron radiation. The spectra have been thoroughly analyzed and transitions up to J=65 and K_a=33 have been assigned. The upper-state rotational levels were fitted using an A-type Watson Hamiltonian written in the I^r representation. An accurate band center ν₀ (ν₉)=369.228080(25) cm⁻¹ as well as accurate rotational and centrifugal distortion constants have been obtained and used to simulate a synthetic spectrum. These parameters should be useful to simulate hot bands of propane involving the 9¹ vibrational level as their lower state.     

Influence of Ca additives on the optical and dielectric studies of sol-gel derived PbTiO3 ceramics

Sintered ceramic powders of calcium-doped lead titanate [Pb_1−xCa_xTiO₃] ceramics with different Ca dopant concentration in the range (x=0-0.35) have been prepared using a sol-gel chemical route. The sol-gel technique is known to offer better purity and homogeneity, and can yield stoichiometric powders with improved properties at relatively lower processing temperature in comparison to conventional solid-state reaction. X-ray diffraction (XRD) and Raman spectroscopy studies have been carried out to identify the crystallographic structure and phase formation. The infrared absorption spectra in the mid-IR region (400-4000 cm⁻¹) show the band corresponding to the Ti-O bond at ∼576 cm⁻¹ and is found to shift to a higher wave number 592 cm⁻¹ with increasing Ca content. The dielectric properties as a function of frequency, and phase transition studies on sintered ceramic Pb_0.65Ca_0.35TiO₃ has been investigated in detail over a wide temperature range 30-600 °C and the results are discussed.     

Improved rovibrational constants for the ν12 band of C2H3D

The Fourier transform infrared absorption spectrum of the ν₁₂ fundamental band of ethylene-d (C₂H₃D) was recorded at an unapodized resolution of 0.0063 cm⁻¹ in the 1330-1475 cm⁻¹ region. Upper state (ν₁₂ = 1) rovibrational constants inclusive of three rotational, five quartic, and four sextic centrifugal distortion constants were improved by assigning and fitting 1444 infrared transitions using Watson’s A-reduced Hamiltonian in the I^r representation. The present analysis yielded more higher-order upper state constants than previously reported. The rms deviation of the fit is 0.00055 cm⁻¹. Improved ground state rovibrational constants were also determined from the combined fit of 2026 ground state combination differences (GSCD) from the assigned infrared transitions of the ν₁₂, ν₃ and ν₆ bands and 21 microwave frequencies of C₂H₃D. The rms deviation of the GSCD fit is 0.00047 cm⁻¹. The A-type ν₁₂ band is centered at 1400.76262 ± 0.00004 cm⁻¹. Local frequency perturbations were not detected in the analysis. The calculated inertial defect Δ₁₂ is 0.20809 ± 0.00003 μŲ.     

Phase and electrical behaviour in the Bi14W1 − xLaxO24 − 3x/2 system

The compositional and thermal dependencies of phase and electrical behaviour of compositions in the system Bi₁₄W_1 − xLa_xO_{24 − 3x/2} (0.00 < x < 1.00) have been studied by X-ray powder diffraction, differential thermal analysis and a.c. impedance spectroscopy. The system exhibits polymorphism and phase separation, which shows both compositional and thermal dependence. Compositions with x = 0.25 and x = 0.50 exhibit a single phase tetragonal structure at room temperature. In contrast, the x = 0.75 composition at room temperature shows a mixture of a cubic phase and a secondary β-Bi₂O₃ related tetragonal phase. A full solid solution is observed at high temperatures, corresponding to the occurrence of a δ-Bi₂O₃ type phase. The appearance of the various phases correlates well with the observed electrical behaviour. The x = 0.75 composition exhibits exceptionally high conductivity at high temperatures (σ₈₀₀ = 1.34 S cm^− 1), but also shows significant phase separation at lower temperatures.     

Optical properties of samarium doped zinc-phosphate glasses

Samarium doped zinc-phosphate glasses having composition Sm₂O_{3 (x)}ZnO_(60−x) P₂O_{5 (40)} (where x=0.1-0.5 mol%) were prepared by melt quenching method. The density of these glasses was measured by Archimedes method; the corresponding molar volumes have also been calculated. The values of density range from 3.34 to 3.87 gm/cm³ and those of molar volume range from 27.62 to 31.80 cm⁻³. The optical absorbance studies were carried out on these glasses to measure their energy band gaps. The absorption spectra of these glasses were recorded in UV-visible region. No sharp edges were found in the optical spectra, which verifies the amorphous nature of these glasses. The optical band gap energies for these glasses were found to be in the range of 2.89-4.20 eV. The refractive index and polarizability of oxide ion have been calculated by using Lorentz-Lorentz relations. The values of refractive index range from 2.13 to 2.42 and those of polarizability of oxide ion range from 6.51×10⁻²⁴ to 7.80×10⁻²⁴ cm³.     

Assignment, fit, and theoretical discussion of the ν10 band of acetaldehyde near 509 cm

The lowest small-amplitude vibration in acetaldehyde (CH₃CHO) is the in-plane aldehyde scissors mode ν₁₀ at 509 cm⁻¹. This mode lies about 175 cm⁻¹ above the top of the barrier to internal rotation of the methyl group and is relatively well separated from other small-amplitude vibrational states (the next fundamental occurring more than 250 cm⁻¹ higher). It thus provides an excellent example of an isolated small-amplitude fundamental (bright state) embedded in a bath of dark states. Since the bath states at these energies are not too dense, and since they arise purely from states of the large-amplitude torsional vibration of the methyl rotor, a detailed spectroscopic analysis of interactions between the bright state and the bath states should be possible. This paper represents the first step toward that goal. We have assigned several thousand transitions in the ν₁₀ band (J ? 28, K ? 12), and have carried out a simultaneous fit of 2400 of these transitions (J ? 15, K ? 9) with over 8100 transitions to the torsional bath state levels. Three vibration-torsion interactions, which give rise to rather global level shifts of the order of 1 cm⁻¹ in the ν₁₀ levels, have been identified and quantitatively fit. A number of vibration-torsion-rotation interactions, which give rise to localized (avoided-crossing) shifts in ν₁₀ have also been determined. The present analysis indicates the need for reliable spectroscopic information on more of the torsional bath states in the immediate vicinity of the ν₁₀ levels. Possible ways of obtaining such information in future studies are considered.     

Nd-laser irradiations effects and AFM-investigations on structural and surface features of optimally lutetium thorium-co-doped-2212-BSCCO

Lutetium-thorium optimally co-doped sample with general formula Bi_2−x−yLu_xTh_ySr₂Ca₁Cu₂O₈ where x = y = 0.15 mol was selected to be the target for three different doses of Nd-laser beam irradiations the 1st 15 W/cm² for 60 min, 2nd 30 W/cm² for 120 min and 3rd 45 W/cm² for 240 min, respectively. Nd-Laser irradiations doses were monitoring as function of micro-structure, superconducting and structural features of Lu-Th-optimally co-doped 2212-BSCCO. AFM and SE-microscopy were applied to investigate changes occurred in the surface's layers after each Nd-laser irradiation dose. Both of bulk superconductivity and surface resistivity were measured to establish the promotion occurred on the superconducting features due to Nd-laser irradiation doses.     

The ν2+ν4 Band of Carbonyl Fluoride

We have measured and fitted over 600 lines in the ν₂+ν₄ combination band of COF₂. The spectrum is well reproduced by extrapolation of rotational constants from the ν₂ and ν₄ fundamentals, with no evidence of significant perturbation. The band centre of 2195.272 15(11) cm⁻¹ permits an estimate of −11.32 cm⁻¹ for the anharmonicity constant x₂₄.     

The effect of Te doping on the electronic structure and thermoelectric properties of SnSe

SnSe_1−xTe_x (x=0, 0.0625) bulk materials were fabricated by melting Sn, Se and Te powders and then hot pressing them at various temperatures. The phase compositions of the materials were determined by X-ray diffraction (XRD) and the crystal lattice parameters were refined by the Rietveld method performed with DBWS. XRD analysis revealed that the grains in the materials preferentially grew along the (l 0 0) directions. The structural behavior of SnSe_1−xTe_x (x=0, 0.0625) was calculated using CASTEP package provided by Materials Studio. We found that the band gap of SnSe reduced from 0.643 to 0.608 eV after Te doping. The calculated results were in good agreement with experimental results. The electrical conductivity and the Seebeck coefficient of the as-prepared materials were measured from room temperature to 673 K. The maximum power factor of SnSe is ∼0.7 μW cm⁻¹K⁻² at 673 K.     

Effect of Sn-doping on the structural,magnetic and magnetocaloric properties of La0.67Ba0.33Mn1−xSnxO3 compounds

Magnetocaloric effect (MCE) in fine-grained perovskite manganites of the type La_0.67Ba_0.33Mn_1−xSn_xO₃ (x=0.05, 0.1 and 0.15) were prepared by the solid-state method. The prepared samples remain single phase and exhibit paramagnetic to ferromagnetic phase transition (T_C) at 340, 325 and 288 K for x=0.05, 0.1 and 0.15, respectively. From the measured magnetization data of La_0.67Ba_0.33Mn_1−xSn_xO₃ compounds as a function of field (2 T), the associated magnetic entropy change close to their respective Curie temperatures and the relative cooling power (RCP) have been determined. Large MCE has been obtained in all samples and |ΔS_M|_max reached the highest value of 2.49 J/kg K at T_C (288 K) for the sample x=0.15, with H=2 T.     

Structural and magnetic properties of nanocrystalline stannic substituted cobalt ferrite

The structural and magnetic properties of the spinel ferrite system Co_1+xFe_2−2xSn_xO₄ (x=0.0–1.0) have been studied. Samples in the series were prepared by the ceramic technique. The structural and microstructural evolutions of the nanophase have been studied using X-ray powder diffraction and the Rietveld method. The refinement result showed that the type of the cationic distribution over the tetrahedral and octahedral sites in the nanocrystalline lattice is partially an inverse spinel. Far infrared absorption spectra show two significant absorption bands, around 600 cm⁻¹ and 425 cm⁻¹, which are respectively attributed to tetrahedral (A) and octahedral [B] vibrations of the spinel. Scanning Electron Microscopy (SEM) was used to study surface morphology. SEM images reveal particles in the nanosize range. The transmission electronic microscope (TEM) reveals that the grains are spherical in shape. TEM analysis confirmed the X-ray results. The magnetic properties of the prepared samples were characterized by using a vibrating sample magnetometer.     

Magnetostriction, Curie temperature and microstructure of Tb0.29(Dy1−xPrx)0.71Fe1.97 oriented alloys

The Tb_0.29(Dy_1−xPr_x)_0.71Fe_1.97 (x=0, 0.1, 0.2 and 0.3) alloys were prepared by directional solidification method. The orientation, magnetostriction λ, Curie temperature T_c and microstructure of alloys were characterized by XRD, standard resistant strain gauge technique, VSM and SEM-EDS. The results reveal that the alloys have a preferred orientation of 〈1 1 0〉 and 〈1 1 3〉 direction when x>0. With the increase in Pr content, the T_c of alloys decreases gradually and the non-cubic phase appears, resulting in the decline of λ dramatically, from 1935.2×10⁻⁶ for x=0 to 695.9×10⁻⁶ for x=0.3 at a compressive stress of 6 MPa and a magnetic field of H=240 kA m⁻¹.     

Single crystal EPR and optical absorption study of Cr doped l-histidine hydrochloride monohydrate

EPR study of the Cr³⁺ ion doped l-histidine hydrochloride monohydrate single crystal is done at room temperature. Two magnetically inequivalent interstitial sites are observed. The hyperfine structure for Cr⁵³ isotope is also obtained. The zero field and spin Hamiltonian parameters are evaluated from the resonance lines obtained at different angular rotations and the parameters are: D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.9108±0.0002, g_y=1.9791±0.0002, g_z=2.0389±0.0002, A_x=(252±2)×10⁻⁴ cm⁻¹, A_y=(254±2)×10⁻⁴ cm⁻¹, A_z=(304±2)×10⁻⁴ cm⁻¹ for site I and D=(300±2)×10⁻⁴ cm⁻¹, E=(96±2)×10⁻⁴ cm⁻¹, g_x=1.8543±0.0002, g_y=1.9897±0.0002, g_z=2.0793±0.0002, A_x=(251±2)×10⁻⁴ cm⁻¹, A_y=(257±2)×10⁻⁴ cm⁻¹, A_z=(309±2)×10⁻⁴ cm⁻¹ for site II, respectively. The optical absorption studies of single crystals are also carried out at room temperature in the wavelength range 195-925 nm. Using EPR and optical data, different bonding parameters are calculated and the nature of bonding in the crystal is discussed. The values of Racah parameters (B and C), crystal field parameter (Dq) and nephelauxetic parameters (h and k) are: B=636, C=3123, Dq=2039 cm⁻¹, h=1.46 and k=0.21, respectively.