Assignments of Carbon-Sulphur Vibrations by Selenation: An FT-IR and FT-Raman Study on 1, 3, 5-Trithiacyclohexane

Abstract

The IR and Raman spectra of 1, 3, 5-trithiacyclohexane (1) and 1, 3, 5-triselenocyclohexane (2) have been recorded with FT-instrumentation within 3500–100 cm^?l, and the C-S vibrations of 1 have been reviewed by comparing its spectra with those of 2. The IR and Raman spectra slightly differ from those previously reported and some vibrations, previously assigned to C-H modes in 1on the basis of NCT calculations, are reassigned to C-S modes on the basis of the selenation effect. “Selenation” has proved to be a very simple and effective tool in recognizing carbon-sulfur vibrations both in IR and Raman. The Raman peaks due to carbon-chalcogen vibrations are less intense in 1 than in 2, according to the higher polarizability of the selenium atom.     

Pressure dependence of electronic transitions of Fe,Co and Ni ions in layered dihalides

Abstract

The near infra-red absorption peaks due to transition metal ions in four halides of Fe, Co and Ni have been studied as a function of pressure. The behaviors of these ions' absorption peaks under pressure are found to be quite different. While the energy of the absorption peak in Col₂ increases with pressure similar to the behavior of transition metal ions in cubic crystal fields, the absorption peaks in the Fe halides are found to be almost independent of pressure. In Nil₂ two absorption peaks exhibit level-crossing at about 2GPa. The results have been interpreted in terms of a theory proposed by da Silva and Falicov [Phys. Rev. B 45,11511 (1992)] in which pressure changes the trigonal component of the crystal field at the transition metal ions.     

Interplay of structural, magnetic and transport properties in thelayered Co-based perovskite LnBaCo 2 O 5 (Ln = Tb, Dy, Ho)

The oxygen deficient cobaltites LnBaCo₂O₅ (Ln = Tb, Dy, Ho) exhibit two successive crystallographic transitions at T _N ∼340 K and at T _CO ∼210 K. Whereas the first transition (P4/mmm to Pmmm) is related to the long-range antiferromagnetic ordering of the Co ions (spin ordering), the second transition (Pmmm to Pmmb) corresponds to the long-range ordering of the Co²⁺ and Co³⁺ species (charge ordering) occurring in 1:1 ratio in the structure. The charge ordered (CO) state was directly evidenced by the observation of additional superstructure peaks using neutron and electron diffraction techniques. The CO state was also confirmed indirectly from refinement of high resolution neutron diffraction data as well as from resistivity and DSC measurements. From the refined saturated magnetic moment values only, ∼3.7 and ∼2.7 , the electronic configuration of the Co ions in LnBaCo₂O₅ remains conjectural. Two pictures, with Co³⁺ ions either in intermediate spin state ( t ⁵ _2g e ¹ _g ) or in high spin state ( t ⁴ _2g e ² _g ), describe equally well our experimental data. In both cases, the observed magnetic structure can be explained using the qualitative Goodenough-Kanamori rules for superexchange. Finally, in contrast to the parent Ln = Y compound [Vogt et al. , Phys. Rev. Lett. 84, 2969 (2000)], we do not report any spin transition in LnBaCo₂O₅ (Ln = Tb, Dy, Ho). Received 13 December 2000     

Splitting of NMR signals in parallel fields in the easy-plane antiferromagnet FeBO3

Experimental observations are reported of the splitting of NMR lines of ⁵⁷Fe into two absorption peaks in a static magnetic field H ₀ parallel to a variable field H ₁ in the basis plane. The field dependence of the intensity and the variation in the resonance frequencies of the absorption peaks with H ₀ are studied. These results can be used to explain some features of the layered domain structure of iron borate. Fiz. Tverd. Tela (St. Petersburg) 41, 290–292 (February 1999)     

Visual and Automatic Evaluation of Vocal Fold Mucosal Waves Through Sharpness of Lateral Peaks in High-Speed Videokymographic Images

IntroductionThe sharpness of lateral peaks is a visually helpful clinical feature in high-speed videokymographic (VKG) images indicating vertical phase differences and mucosal waves on the vibrating vocal folds and giving insights into the health and pliability of vocal fold mucosa. This study aims at investigating parameters that can be helpful in objectively quantifying the lateral peak sharpness from the VKG images.MethodForty-five clinical VKG images with different degrees of sharpness of lateral peaks were independently evaluated visually by three raters. The ratings were compared to parameters obtained by automatic image analysis of the vocal fold contours: Open Time Percentage Quotients (OTQ) and Plateau Quotients (PQ). The OTQ parameters were derived as fractions of the period during which the vocal fold displacement exceeds a predetermined percentage of the vibratory amplitude. The PQ parameters were derived similarly but as a fraction of the open phase instead of a period.ResultsThe best correspondence between the visual ratings and the automatically derived quotients were found for the OTQ and PQ parameters derived at 95% and 80% of the amplitude, named OTQ₉₅, PQ₉₅, OTQ₈₀ and PQ₈₀. Their Spearman's rank correlation coefficients were in the range of 0.73 to 0.77 (P < 0.001) indicating strong relationships with the visual ratings. The strengths of these correlations were similar to those found from inter-rater comparisons of visual evaluations of peak sharpness.ConclusionThe Open time percentage and Plateau quotients at 95% and 80% of the amplitude stood out as the possible candidates for capturing the sharpness of the lateral peaks with their reliability comparable to that of visual ratings.     

Ionic,electronic and ion-diffusion controlled relaxation processes in CaF2, BaF2 and LiBaF3 crystals

Abstract

The ionic, electronic and anion-diffusion controlled thermally stimulated relaxation (TSR) processes at 80—700 K in CaF₂ BaF₂ and LiBaF₃ crystals (X-ray irradiated or non-irradiated) have been investigated by means of ionic conductivity, ionic thermally stimulated (TS) depolarization current (TSDC); as well as current (TSC), luminescence (TSL) and bleaching (TSB) techniques. Above 250—290 K broad and overlapping anion TSDC peaks and correlated TSB stages are detected. The TSB kinetics is initiated and controlled by anion detrapping and interaction with the localized charges, i.e., the anion-diffusion controlled TSR processes take place in fluorides. The TSL and TSC data for LiBaF₃ indicate that the lifetime and drift of electrons at 80—250 K is very small because of deep retrapping. The main TSL peaks at 132K, 170K and 220 K are caused by V_k center detrapping and hole-diffusion controlled tunnel recombination within pairs like {D_n e^?…V_k }.     

Thermoluminescence of nominally pure KTaO 3 crystals

After an exposure to ultraviolet light ( u <350 v nm) at 12 v K, weak thermoluminescence of nominally pure KTaO 3 crystals was observed within the temperature region from 13 to 65 v K for the first time. An analysis of the glow curves of integral thermoluminescence revealed five glow peaks with markedly sample-dependent intensities. Three glow peaks near 26, 31, and 58 v K at the heating rate of 0.155 v K/s correspond to thermoluminescence spectrally very similar to broad-band visible photoluminescence. The glow peaks near 26 and 31 v K were assigned to the electron release from photoinduced Ta 4+ -OH m and Ta 4+ - V O centers and the glow peak near 58 v K to the hole release from photoinduced O m centers. The glow peaks near 34 and 41 v K are connected with the structureless emission band peaking near 714 v nm at 15 v K that was observed in the emission spectra of KTaO 3 crystals for the first time.     

Effects of Gd<Superscript>3+</Superscript> doping on structural and dielectric properties of PZT (Zr:Ti = 52:48) piezoceramics

The purpose of this research is to study the effect of doping Gd into Pb(Zr_0.52Ti_0.48)O₃ ceramics prepared by solid state reaction. X-ray diffraction patterns show that all PGZT samples are of tetragonal structure and the highest doping should be no more than 2 mole % Gd at which the unreacted oxides start to appear. The electron spin resonance (ESR) spectra of PGZT's indicate that Gd³⁺ can enter both A site of the perovskite structure instead of only A site as widely believed. The ESR peaks resonance shift towards low fields as the concentration is higher, which is due to the change in crystal field experienced by Gd³⁺ ions. At x =0.001, 0.005 and 0.01 dopings, two sets of powder ESR signals arising from Gd³⁺ (4f⁷, spin 7/2) ions at A site. The first set shows some fine structure having strong absorption peaks centered at 76.26 mT (g = 8.550). The second is a seven-peak spectrum centered at 206.01 mT (g = 3.165), which belongs to the Gd³⁺ ions at B sites. Furthermore, the overlapped ESR strong absorption peaks from 309.17 mT to 314.49 mT (g = 2.2818-2.1087) belong to Gd³⁺ of unreacted Gd₂O₃. The local environments of Gd³⁺ ions were verified from the calculated ESR spectra using appropriate spin Hamiltonian parameter, i.e. gyromagnetic tensor g, zero-field splitting D and hyperfine tensor A.     

Pressure Induced Phase Transition in Solid Oxygen at 1.8 K

Pressure dependence of Raman scattering in solid oxygen was studied at 1.8 K. When the f phase is compressed, two libron peaks that, increasing pressure, merge smoothly with those of the l phase at 8 GPa are observed around 5 GPa, besides the libron peaks due to the f phase. Furthermore, unknown Raman peaks are also observed at 5-9 GPa. Coexistence of these Raman peaks indicates that the pressure region from 5 to 9 GPa at low temperature does not correspond to a single phase but complicated mixed ones including f and l components.     

Influence of spin–orbit interaction,Zeeman effect and light polarisation on the electronic and optical properties of pseudo-elliptic quantum rings under magnetic field

ABSTRACT

We theoretically investigated the influences of the magnetic field and light polarisation on the electronic and optical properties of a GaAs/GaAlAs pseudo-elliptic quantum ring, modelled by an outer ellipsis and an inner circle, in the presence of the Rashba and Dresselhaus spin–orbit interactions and Zeeman effect. We show that Aharonov-Bohm oscillations of the energy spectrum are not affected by the presence of the Zeeman effect alone but, in the presence of Rashba and Dresselhaus spin–orbit couplings, the periodicity of certain levels becomes hardly definite. The Zeeman effect generally enhances/diminishes the separation levels produced by Rashba/Dresselhaus interactions (SOI) and when both types of SOI are considered, the effect depends on their relative strength. The magnetic field can trigger spin-flip for each type of spin–orbit interaction and Zeeman effect or their combination through anticrossings in the energy spectra. Our results reveal that the absorption spectra are very sensitive to the magnetic field and light polarisation. For all polarisations considered, the magnetic field increment leads to the redshift or blueshift of some particular peaks (an effect of this ring geometry) and a better separation of the peaks. The x-polarised light determines spectra with many small, but separated peaks while the circular polarised light leads to spectra with large peaks of high amplitude.     

A Practical Method for the Analysis of Overlapped Peaks in Energy Dispersive X-Ray Spectra

ABSTRACT

In this study a practical method for the spectral analysis of some overlapped characteristic X-ray peaks is presented. The overlapped characteristic K, and K, peaks and the artificially overlapped two K, peaks (peak doublet) of arsenic obtained by the radioisotope-excited, energy dispersive X-ray fluorescence (EDXRF) technique, are resolved. A total of 34 overlapped peak systems were investigated: the proposed method provided 18 reliable results, whereas the first and the second methods gave 15 and 1, respectively. The intensity ratios of K_β/K_α, obtained by the novel method are also in good agreement with the theoretical relativistic Hartree-Slater values.     

Wavevector-Dependent Susceptibility in <Emphasis Type="Italic">Z</Emphasis>-Invariant Pentagrid Ising Model

We study the q-dependent susceptibility χ(q) of a Z-invariant ferromagnetic Ising model on a Penrose tiling, as first introduced by Korepin using de Bruijn's pentagrid for the rapidity lines. The pair-correlation function for this model can be calculated exactly using the quadratic difference equations from our previous papers. Its Fourier transform χ(q) is studied using a novel way to calculate the joint probability for the pentagrid neighborhoods of the two spins, reducing this calculation to linear programming. Since the lattice is quasiperiodic, we find that χ(q) is aperiodic and has everywhere dense peaks, which are not all visible at very low or high temperatures. More and more peaks become visible as the correlation length increases—that is, as the temperature approaches the critical temperature. Supported in part by NSF Grant No. PHY 01-00041.     

Detection of fatty acid composition of trabecular bone marrow by localized iDQC MRS at 3 T: A pilot study in healthy volunteers

BackgroundAlthough a growing body of research shows that the bone marrow adipose tissue (BMAT) may play an essential role in bone inflammation and energy metabolism, available noninvasive methods for distinguishing different fatty acids in BMAT are still limited, in spite of their potential to provide novel biomarkers for bone related diseases.PurposeTo assess the ability of a localized intermolecular double quantum coherence (iDQC) spectroscopy sequence to resolve more fatty acid peaks than conventional MR spectroscopy (MRS), like polyunsaturated fatty acids (PUFA), from the human BMAT in the presence of trabecular bone; To preliminarily investigate whether the fatty acids composition is different between different regions and groups.ResultsCompared with conventional MRS results, additional four fatty acids peaks were well resolved using the proposed method in human BMAT in the presence of trabecular bone. In addition, a different fat composition was found between distal femur and proximal tibia: fat was more unsaturated (vinyl, *p < 0.01; diallylic, *p < 0.01) in distal femur bone marrow than in proximal tibia, and this higher unsaturation level was caused by PUFA (r = 0.67, diallylic, *p < 0.01). No significant difference in fatty acid composition were found either between left and right legs, or between female and male in the healthy young subjects studied.ConclusionThis study demonstrated that the unsaturated fatty acids information of human BMAT in the presence of trabecular bone can be clearly identified with the localized iDQC at 3 T. The resolved peaks, especially PUFA, may serve as additional diagnostic biomarkers for BMAT related diseases in the future.     

Substituent effect on the electrochemical behaviour of some ortho-substituted (aryl)(2-nitrobenzo[ b ]thiophen-3-yl)amines. A combined experimental and computational study

The reduction potential values of the title compounds (1Ar,o) have been evaluated by cyclic voltammetry at a platinum electrode in the presence of 0.1?M N(Et)₄BF₄ in DMSO. Compounds 1Ar,o give reversible reduction peaks. The ortho-substituent affects their values basically by electronic effects (good LFER have been observed). The peculiar behaviour of (2′-hydroxyphenyl)(2-nitrobenzo[b]thiophen-3-yl)amine 1Ar,o(i) (showing two quasi reversible systems of peaks) has been explained on the basis of the special effect of the 2′-hydroxy substituent, which is able to assist a proton transfer through a network of hydrogen bonds involving the amine nitrogen atom (proton shuttle). This behaviour is unexpected in anhydrous DMSO and has similarities with the reaction features observed in water. The above hypothesis has been confirmed by quantum-mechanical DFT calculations carried out on 1Ar,o(i). In this theoretical investigation all the possible species, that can form as a consequence of two mono-electron reduction processes and the relevant various chemical transformations involving the intermediate species, have been carefully investigated.     

Relative thermoluminescence effects of alpha‐ and beta‐ radiation

Abstract

A study has been made of the relative thermoluminescence response to α- and β-radiation of six phosphors (two types of natural fluorite, CaF₂: Mn, CaF₂: Tb, CaSO₄: Mn and quartz) using samples which are thin compared to the range of the α-particles. The α- and β-radiations induce the same glow peaks, but at low doses (<100 rads) the TL response per rad of α-radiation (3.7 MeV) is less than that per rad of β-radiation in all the glow peaks studied. The α-efficiency ranges from 53 per cent for CaF₂: Mn to 2 per cent for quartz (110°C peak) at 3.7 MeV and decreases with decreasing α-particle energy. At higher doses (10⁶?10⁷ rads) the TL responses to α- and β-radiation become equal within 15 per cent; most of the glow peaks are in or near saturation at these doses. The higher the β-dose at which a peak saturates, the higher is the α-efficiency (at low doses) of that peak. The results support the interpretation that the α-efficiency is low because the phosphor is near or in saturation in the localized region near the α-path. This interpretation is given quantitative support by a theoretical calculation of the localized energy-density.     

Effects of pre-irradiation treatment on EPR,optical absorption and TL of albite

In the present work pre-irradiation annealing effect was investigated in albite, NaAlSi 3 O 8 , a silicate crystal. Albite powder samples were heated at 500, 600, 700, 800 and 900 v C for 40 minutes, and then submitted to n -irradiation. Results show that first TL peak (around 160 v C) decreases with annealing temperature, while higher temperature peaks strongly increase. EPR signal around g factor 2, attributed to Al-O m -Al centers, increase with annealing temperature too, as well as optical absorption bands that appear in the crystal after relatively strong n -dose irradiation (of some kGys).     

Decoupling multimode vibrational relaxations in multi-component gas mixtures: Analysis of sound relaxational absorption spectra

Decoupling the complicated vibrational-vibrational (V-V) coupling of a multimode vibrational relaxation remains a challenge for analyzing the sound relaxational absorption in multi-component gas mixtures. In our previous work [Acta Phys. Sin. 61 174301 (2012)], an analytical model to predict the sound absorption from vibrational relaxation in a gas medium is proposed. In this paper, we develop the model to decouple the V-V coupled energy to each vibrational- translational deexcitation path, and analyze how the multimode relaxations form the peaks of sound absorption spectra in gas mixtures. We prove that a multimode relaxation is the sum of its decoupled single-relaxation processes, and only the decoupled process with a significant isochoric-molar-heat can be observed as an absorption peak. The decoupling model clarifies the essential processes behind the peaks in spectra arising from the multimode relaxations in multi-component gas mixtures. The simulation validates the proposed decoupling model.     

Characteristics of the elastic strain of a Ge(111) surface under a mechanical load

Estimates are obtained for various components of the elastic strain in a Ge(111) surface layer under isotropic lateral tension. Agreement with the reversible components of surface thinning, derived from energy shifts in the volume and surface plasma peaks, suggests that the latter have an elastic character. It is conjectured that the anomalously high strain in a thin surface layer is due to the partially quasielastic variation of the relief of strained semiconductor surfaces. Fiz. Tverd. Tela (St. Petersburg) 41, 641–644 (April 1999)     

A hybrid-phonon resonance in a quasi-two-dimensional nanostructure

The coefficient of absorption of electromagnetic radiation by a quasi-two-dimensional electron gas placed in an oblique magnetic field is found. The scattering of electrons by optical phonons is shown to lead to resonant absorption. The shape of the resonance peaks on the absorption curve is studied, and their doublet nature is demonstrated. Finally, the dependence of the resonance peaks on the angle between the magnetic field vector and the confinement plane is investigated. Zh. éksp. Teor. Fiz. 111, 1092–1106 (March 1997)     

Precise measurement of hyperfine structure in the state of Rb

We demonstrate a technique to measure hyperfine structure using a frequency-stabilized diode laser and an acousto-optic modulator locked to the frequency difference between two hyperfine peaks. We use this technique to measure hyperfine intervals in the 5 P _3/2 state of ⁸⁵Rb and obtain a precision of 20 kHz. We extract values for the magnetic-dipole coupling constant A = 25.038(5) MHz and the electric-quadrupole coupling constant B = 26.011(22) MHz. These values are a significant improvement over previous results. Received 6 March 2003 Published online 15 April 2003