Electronic and thermodynamic properties of α-Pu2O3

Based on density functional theory+U$\text{density functional theory}+U$ calculations and the quasi-annealing simulation method, we obtain the ground electronic state for α-Pu₂O₃ and present its phonon dispersion curves as well as various thermodynamic properties, which have seldom been theoretically studied because of the huge unit cell. We find that the Pu–O chemical bonding is weaker in α-Pu₂O₃ than in fluorite PuO₂, and subsequently a frequency gap appears between oxygen and plutonium vibration density of states. Based on the calculated Helmholtz free energies at different temperatures, we further study the reaction energies for Pu oxidation, PuO₂ reduction, and transformation between PuO₂ and α-Pu₂O₃. Our reaction energy results are in agreements with available experiment. And it is revealed that high temperature and insufficient oxygen environment are in favor of the formation of α-Pu₂O₃.     

Tight-binding parameterization of α-Sn quasiparticle band structure

The diamond structure of tin (α-Sn) can be stabilized in nanocrystals embedded in a suitable host. We developed highly accurate parameterizations for tight-binding simulation of such structures incorporating strain and spin-orbit interaction. Parameters are obtained by fitting to ab initio GW quasiparticle band structures of unstrained α-Sn as well as geometries under uniform compressive or tensile strain. The optical response calculated from this fit is in excellent agreement with experiments. As an application, confinement induced band gaps in strained and unstrained 3 nm nanocrystals are computed. It is found that compressive and tensile strain raises and lowers the gap, respectively.     

On κ-deformation and triangular quasibialgebra structure

We show that, up to terms of order κ⁻⁵${\kappa }^{\mathrm{-5}}$, the κ-deformed Poincaré algebra can be endowed with a triangular quasibialgebra structure. The universal R matrix and coassociator are given explicitly to the first few orders. In the context of κ-deformed quantum field theory, we argue that this structure, assuming it exists to all orders, ensures that states of any number of identical particles, in any representation, can be defined in a κ-covariant fashion.     

AC-conductivity and Raman spectra of polyiodide inclusion compounds (β-cyclodextrin)2·KI7·16H2O and (β-cyclodextrin)2·LiI7·14H2O during the dehydration process

The frequency and temperature dependence of ac-conductivity and phase shift of polycrystalline inclusion compounds (β-CD)₂·KI₇·16H₂O and (β-CD)₂·LiI₇·14H₂O (β-CD=β-cyclodextrin) has been investigated over the frequency and temperature ranges of 0-100 kHz and 240-420 K. A Raman spectroscopic study and calorimetric measurements are also accomplished. The Arrhenius exponential behaviour of the ac-conductivity for T>275 K is caused by the contribution of the metal cations K⁺, Li⁺. This contribution is facilitated by the water-net via the Grotthuss mechanism. The ac conductivity starts deviating from the exponential behaviour with lower increasing rate, at 347 K for β-K and at 353 K for β-Li reaching a maximum value at 371.1 and 361.8 K, respectively, and then decreases rapidly due to the gradual removal of all the water molecules. The values 371.1 and 361.8 K are characterized as semiconductor to metal transition temperatures. The shift of the initial Raman peak at 179 cm⁻¹ to the final value 165 cm⁻¹ as the temperature increases reveals the lengthening of I₂ units via a charge transfer interaction in I⁻₇ units. A second topical maximum value of conductivity appears at 399.7 K for β-K and 403 K for β-Li, attributed to the sublimation of I₂.     

Photonic band structure and effect of ε and μ on the reflectivity of one-dimensional magnetic photonic crystal structure

In this paper, we study the photonic band structure and reflection properties in one-dimensional magnetic photonic crystals (MPCs). Investigation of dispersion characteristics shows that in the case of MPCs, photonic band gaps arise due to the contrast in the wave impedance, not due to the contrast in the refractive index, while contrast in the refractive index of the two layers decides the position and number of the band gaps. We also study the effect of permittivity and permeability on reflection bands, which shows that the structure that has larger values of magnetic permeability (μ) than dielectric permittivity (ε) have wider TM-reflection bands, whereas the structure for which ε is greater than μ has wider TE-reflection bands. But the gap to mid-gap frequency ratio for TM-reflection bands is larger than TE-reflection bands. Thus, magnetic permeability has greater impact on the reflectivity of MPCs than dielectric permittivity. Finally, the analysis of the omni-reflectance in MPCs has also been studied.     

Theoretical investigation on the optical absorption spectra and local lattice structure of α-Al2O3:Yb crystals

In this paper, the optical absorption spectra of Yb³⁺ in the α-Al₂O₃ crystal are reasonably explained by using the superposition model and local lattice structure analysis. Based on these studies, we find that the local geometrical structure around the Yb³⁺ ions possesses an elongated trigonal distortion above the O²⁻-triangle and a compressed trigonal distortion in the lower one.     

Electronic and crystal structure of α- and β-CeIr2Si2

We present the results of XRD, magnetization, resistivity and specific heat measurements of CeIr₂Si₂ single crystals for both, the low-temperature α-phase and the high-temperature β-phase, respectively. The α-phase adopts the tetragonal ThCr₂Si₂-type whereas the β-phase forms in the CaBe₂Ge₂-type structure. Both the phases remain paramagnetic down to low temperatures, nevertheless both, the magnetization and resistivity exhibit pronounced anisotropy in the whole temperature range of measurements (2-300 K). Results of fitting the temperature dependence of the susceptibility within the interconfiguration-fluctuation model point to the Ce valence fluctuating between 3+ and 4+. The α-phase behaves as a Fermi-liquid (FL) at low temperatures whereas the β-phase exhibits non-Fermi-liquid (NFL) features. The results are discussed in context of other similar polymorphic compounds.     

Controlled drug release applications of the inclusion complex of peracetylated-β-cyclodextrin and water-soluble drugs formed in supercritical carbon dioxide

Supercritical carbon dioxide (scCO₂) processing was performed with mixtures of CO₂-soluble peracetylated-β-cyclodextrin (PAc-β-CD) heptakis(2,3,6-tri-O-acetyl)-β-cyclodextrin, and highly water-soluble drug molsidomine (MOL) to prepare inclusion complexes of MOL and PAc-β-CD. The MOL/PAc-β-CD inclusion complex was confirmed by differential scanning calorimetry, X-ray diffractometry, and ¹H NMR analyses. The complexes were further investigated for their potential use in controlled drug delivery applications. The in-vitro release of MOL from the peanut oil suspensions into aqueous phase was found to be significantly retarded by the complexation with PAc-β-CD, mainly due to the hydrophobic properties associated with the PAc-β-CD.     

The property of κ-deformed statistics for a relativistic gas in an electromagnetic field: κ parameter and κ-distribution

We investigate the physical property of the κ parameter and the κ-distribution in the κ-deformed statistics, based on Kaniadakis entropy, for a relativistic gas in an electromagnetic field. We derive two relations for the relativistic gas in the framework of κ-deformed statistics, which describe the physical situation represented by the relativistic κ-distribution function, provide a reasonable connection between the parameter κ  , the temperature four-gradient and the four-vector potential gradient, and thus present for the case κ≠0$\kappa \ne 0$ one clearly physical meaning. It is shown that such a physical situation is a meta-equilibrium state of the system, but has a new physical characteristic.     

First principles study of electronic structure and carrier mobility in β-armchair antimony nanotubes

In recent work, we have investigated the structure and stability of β-armchair antimony nanotubes (SbNT) using density functional theory (DFT). We studied electronic properties like electronic band structure, density of states (DOS) and mechanical properties such as stiffness constant, Poisson's ratio, and mechanical strength for these nanotubes. We found that these nanotubes are energetically stable and semiconducting in nature with band-gap varying between 1.32 eV to 1.47 eV. We have also calculated effective mass and carrier mobility for these nanotubes. Furthermore, stiffness constant and mechanical strength of these nanotubes increases with increase in diameter. While, $(4,4)$ nanotube shows anomalously higher strength than other nanotubes. The results of effective mass and carrier mobility for these nanotubes shows that electrons have higher effective mass and therefore lesser mobility than holes for most of the nanotubes. Our calculations show that β-armchair antimony nanotubes (SbNT) could be use in nano-electronics.     

Structural and superconductivity study on α-FeSex

We have successfully synthesized the α-FeSe_x binary tetragonal superconductors with nominal composition of FeSe_x (x=0.6-1.0) via conventional solid state reactions between Fe and Se sealed in quartz tubes. Fe and β-FeSe are the most commonly seen impurities in this binary system. A low-temperature annealing at 400 °C is found to be crucial to remove β-FeSe, which is the thermodynamic stable phase with hexagonal symmetry. For all the samples of FeSe_x, superconductivity is confirmed by magnetic measurements as well as resistivity measurements with their T_c at around 8 K. We noticed that their T_c does not vary with the different nominal Se amount. High-resolution synchrotron X-ray diffraction analysis revealed that the unit cell parameters of all these samples do not change within the error range, and their structure only tolerate the same very small amount of Se deficiency. Based on this study, we concluded that the α-FeSe_x superconductor only exist in a very narrow deficiency range.     

Correlation between microstructure and first-order magnetization reversal in the SmCo5/α-Fe nanocomposite magnets

SmCo₅/α-Fe nanocomposite magnets with different morphology have been fabricated by ball milling of the micrometer sized SmCo₅ and α-Fe powders. The α-Fe grains vary from elongated nano-strips to spherical nanoparticles with increasing milling time. The inter-phase exchange coupling is enhanced with increasing milling time due to reduced grain size. The first-order reversal curves (FORCs) are taken to identify optimal conditions for exchange coupling. It has been found that the stripped morphology results in weak inter-phase exchange coupling, while enhanced exchange coupling is observed with further reduction of the soft-phase grain size. Compared with the measurement of demagnetization curves, FORC analysis provides more information on the magnetostatic as well as the exchange interactions.     

The ν1, ν4 and 3ν6 bands of methyl chloride in the 3.4-μm region: Line positions and intensities

Methyl chloride (CH₃Cl) is one of the most abundant chlorine-containing molecules in the atmosphere. For this reason a recent update was performed in HITRAN in the 640-2600 cm⁻¹ region based on the line parameters generated in Nikitin et al. [Nikitin A, Champion JP, Bürger H. J Mol Spectrosc 2005;230:174-84] with the intensities scaled to existing experimental data. CH₃Cl has a rather strong signature around 3000 cm⁻¹ which was used recently by the Atmospheric Chemistry Experiment (ACE) satellite mission to produce the first study of the global distribution of methyl chloride in the upper troposphere and stratosphere. However, it was mentioned that the CH₃Cl line positions and intensities spectroscopic parameters are of very low quality in this spectral region in the public access HITRAN or GEISA databases. We present a complete update of the line positions and line intensities for the ν₁, ν₄, 3ν₆ bands of CH₃ ³⁵Cl and CH₃ ³⁷Cl in the 3.4 μm region. For this task, Fourier transform spectra have been recorded at high resolution at the Laboratoire de Dynamique, Interactions et Réactivité in France. Measurements of line positions and line intensities have been retrieved for both isotopologues ¹²CH₃ ³⁵Cl and ¹²CH₃ ³⁷Cl in the ν₁, ν₄, 3ν₆ bands. The theoretical model accounts for the interactions coupling the (ν₁=1; ?=0), (ν₄=1; ?=±1) and (ν₆=3; ?=±1) energy levels, together with additional resonances involving several dark states.     

Study of vibration-rotation levels in formamide with high resolution FTIR spectroscopy: The ν12, 2ν12, ν11, and ν9 bands

The far infrared and infrared spectra of formamide (HCONH₂) have been recorded at high resolution (0.00125 cm⁻¹) in the region of 90-1060 cm⁻¹. Over 20,000 transitions from the out-of-plane NH₂ wagging motion (n₁₂ = 1 ← 0 fundamental, n₁₂ = 2 ← 0 overtone, n₁₂ = 2 ← 1 difference bands), torsion (n₁₁ = 1 ← 0 bands), and out-of-phase NCO/NH₂ bend (n₉ = 1 ← 0 bands) have been assigned. Molecular parameters have been obtained for the ground state and the unperturbed n₁₂ = 1 state. The least-squares fit calculations were completed with the microwave data available in the literature. The complicated resonance system between the n₁₂ = 2, n₁₁ = 1, and n₉ = 1 states has been investigated carefully. Thus, we have been able to verify almost all resonances (avoided crossing) existing in the region J, K investigated. In the coupled Hamiltonian used for the fit, all Watson’s reduced parameters, including the octic ones and 16 Coriolis coupling parameters were taken into account. The rms deviation obtained from the fit was 0.000247 cm⁻¹.     

High resolution FTIR spectroscopy of pentafluoroethane: perturbations in the Coriolis doublet of ν4 and ν13

The FTIR spectrum of pentafluoroethane (R125) was measured in the mid infrared region from 900 to 4000 cm⁻¹. Vibrational assignments for R125 are revised by comparison of previous and current experimental data with ab initio calculations at both the MP2/6-311+(d,p) and B3LYP/TZV+(3df,3p) levels of theory. High resolution FTIR spectra were recorded at room temperature and in an enclosive flow cell at a rotational temperature of 140 K. The cold spectrum was sufficiently resolved to enable rovibrational analyses of the overlapping ν₄ (1200.7341 cm⁻¹) and ν₁₃ (1223.3 cm⁻¹) bands, which have a/c hybrid and b-type character, respectively. Ground state combination differences were used to confirm assignment of 2375 lines to ν₄ (J_max = 86, K_{a max} = 50) and 2921 lines to ν₁₃ (J_max = 60, K_{a max} = 54). Effective rotational and centrifugal distortion constants were determined for ν₄, and the polarization ratio was found to be . Severe Coriolis perturbations prevent any satisfactory fit to the ν₁₃ band.     

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.     

Electronic structure of α-Al2O3 slabs: A local environment study

In this work we performed an ab initio/Density Functional Theory (DFT) study of structural and electronic properties of the (0 0 1) α-Al₂O₃ surface. For this study we used two methods with different basis set: the Full-Potential Augmented Plane Wave plus local orbital (FP-APW+lo) and a linear combination of numerical localized atomic orbital basis sets, employing the WIEN2k code and the SIESTA code, respectively. In order to calculate the structural and electronic properties of the reconstructed surface, we calculated the final equilibrium atomic position with the SIESTA code and then the electric-field gradient (EFG) at Al sites was calculated with the FP-APW+lo code using the optimized positions. Using this procedure we found equilibrium structures with comparative lower energy than those obtained using only the FP-APW+lo method. The EFG tensor and the local structure for Al were studied as a function of the depth from the surface for the relaxed structures. We found that distances down to 6 Å from the surface are sufficient to converge the EFG and the Al–O distances to bulk values. The predicted bulk EFG at the Al site is in good agreement with available experimental values. These results can be used for local probes purposes, e.g., in the case of doping, with important sensitivity for probes located close to the top of the surface, in particular for distances smaller than 6 Å.     

Wideband wavelength conversion using double-pass cascaded χ:χ interaction in lossy waveguides

We report the wavelength conversion based on double-pass cascaded nonlinear interaction (χ⁽²⁾:χ⁽²⁾) of sum and difference frequency generation in quasi-phase matched lithium niobate waveguides and compare it with double-pass cascaded second harmonic generation and difference frequency generation with and without waveguide loss. It is shown that the efficiency decreases considerably even for the low-loss waveguide compared to the lossless one especially for long waveguides and to achieve the higher efficiency for the same length, the amount of the extra power to compensate the loss increases. Also, an increased detuning of pump wavelength is proposed to flatten the response with a small efficiency penalty. The detuning- and loss-compensating pump powers can be found using the design diagrams in which the criteria for the design of waveguide length and the assignment of pumps power to obtain the desired efficiency, ripple and bandwidth are presented assuming a 75-nm pump wavelength difference.