Dielectric relaxation of mixtures of non-rigid polar molecules in benzene

The dielectric absorption of three compositions of Isobutyl-methacrylate and Allyl-methacrylate, both consisting of non-rigid molecules, has been studied at 9.92 GHz over a range of temperatures in the dilute solutions of benzene. The various relaxation times τ_o, τ(1) and τ(2), the distribution parameter, α and the thermodynamic parameters for the activated states, both for relaxation and the viscous flow processes have been determined using the measured dielectric data. The results indicate that the properties of the single component systems, such as existence of intramolecular and overall rotations, and absence of solid rotator phase, are retained in the two component system. The values of molar entropy of activation for the relaxation process indicate that the cooperative orientation of the molecules in the single component system changes into non-cooperative orientation in the binary system. A comparison of the experimental values of the most probable relaxation time τ₀ with those calculated on the basis of simple and reciprocal mixing rules and also by a procedure suggested by M.P. Madan [5] reveals that none of these procedures can successfully predict the experimental data.     

Longitudinal relaxation of Fe nuclei in Yb-doped YIG

Measurements of T₁ for ⁵⁷Fe nuclei in Yb-doped YIG are reported for the temperature range 0·7–140 K, with the magnetization along the [111], [100], [110], and [112] crystallographic directions respectively. The dependence of T₁ on Yb concentration and on the magnitude of the applied field was also studied. These results are interpreted in terms of the ‘slow relaxation theory’, and are correlated with the ferrimagnetic resonance work of Clarke, Tweedale, and Teale, whose data have been reanalyzed by us. Both sets of data can be represented fairly well by the theory, with a consistent set of relevant parameters. However, the tensor G which describes the splitting of the Yb ground-state doublet must be modified somewhat from that deduced by Clarke et al., the new principal values being G₁ = 29·0 cm⁻¹, G₂ = 20·4 cm⁻¹ and G₃ = 8·5 cm⁻¹ respectively. Below approximately 10 K, when the magnetization is in the [110] or [112] direction, the nuclear relaxation rate is higher than predicted. These anomalies correspond to those observed in ferrimagnetic resonance line width, which have been attributed to Yb ions on the octahedral lattice sites normally occupied by iron. Anomalously large values of T⁻¹₁ are also observed below approximately 4 K in the [111] and [100] directions, and these remain to be accounted for.     

Generalized susceptibilities and phonon anomalies in Pd and Pt metals

The generalized susceptibility, χ(q), in Pd and Pt for q along the [100], [110], [111], and [120] directions was determined from their APW and RAPW energy band structures, respectively, using the analytic tetrahedron linear energy scheme of Rath and Freeman. The band structures were previously found to yield Fermi surface radii, temperature dependencies of the static magnetic susceptibility, χ(T), resistivity, and a spin lattice relaxation, T₁T, in very good agreement with experiment. In the χ(q) calculations, we used 2048 tetrahedra in 1/48th irreducible BZ and the energy eigenvalues for bands 4, 5, and 6 which cross the Fermi energy as fitted to a Fourier series representation. The intraband parts of χ(q) at q = 0 for both metals are found to agree with the density of states at the Fermi energy to without 0.5%. Our results show that the dominant contribution to χ_intra arises from the dominant band 5 whose “jungle-gym” FS has strong nesting features; the main peak for Pd occurs at the same q value (= 0.65π/a) for q along the [0q0], [q, q, 0], and [q, q, q] directions. The locus of this main peak is a square in the (0, 0, 1) plane. The maximum of χ_intra for q along the [110] and [111] directions are 23% and 13%, respectively, higher than the value of χ(q) at q = 0. For q along the [010] and [120] directions, the peak is, however, lower than the value of χ_intra at q = 0. Hence, while phonon anomalies are predicted for the [110] and [111] directions, no anomaly is predicted for either the [100] or [120] direction. The predicted q value for the [110] anomaly, $\text{q}\text{= 0.65π/a}$ is close to the experimental value of ～0.7 π/a. Although there may be a hint of an anomaly at 0.56 [111] in the measurements, a more detailed investigation of this region is called for. For platinum, χ_intra for q along the [010], [110] and [111] directions has main peaks which occur at q = 0.68 π/a, 0.75 π/a, and 0.85 π/a, respectively. Here too, this main peak comes from the nesting of the jungle-gym Fermi surface which is not, however, as flat as that of palladium. Anomalies are predicted (although weaker in Pt than in Pd) along [110] and [111] but not along [100] and [120]. The [110] anomaly is close to the measured q value (～0.7–0.8 π/a). Also in agreement with experiment, we predict a weaker [110] anomaly for Pt than for Pd. In both Pd and Pt, weaker anomalies are predicted for the [111] direction than for the [110] direction.     

On the Fate of Methanol and Ethanol in Cotton Plant

O-Methylester groups constitute a part in a variety of well-known organophosphorus insecticides. Such compounds, e.g. Dipterex and Rogor [1], were found to undergo in vivo [2–4] as well as in vitro [5]P—OCH₃ cleavage, thus liberating methanol. The degradation of methanol in mammals has been extensively studied [6, 7] and more recently its fate in the cotton leaf worm has been investigated [8].     

Theoretical study of the 5p56s – 5p6 spectra of neutral xenon

Recent high precision measurements on the lifetime of the metastable 6s[3/2]₂ state of atomic xenon display a difference with previous predictions by a factor of 2–3. In the present work, a systematic relaxation and correlation approach, which has been developed on the basis of a widely used multi-configuration Dirac-Fock method, is applied to study the electric dipole allowed E1 and forbidden M1, E2 and M2 transitions between the 5p⁵ 6s and 5p⁶ configurations. We systematically include the correlation effects which arise from all the single and double excitations from the occupied shells into the (n=6–10) active sets and the relaxation effects caused by change of the electron density between the radiative initial- and final-states. This study not only reduces greatly the existing discrepancy in the lifetime of the 6s[3/2]₂ state, but also presents rather consistent results for both the lifetime of the metastable 6s'[1/2]₀ state and the oscillator strength of the 5p⁵ 6s - 5p⁶ E1 resonant transitions.     

Proton states in193Ir and195Ir populated via the (α) reaction

The nuclear structures of¹⁹³Ir and¹⁹⁵Ir have been studied using the¹⁹⁴Pt(t, α) and¹⁹⁶Pt(t, α) reactions. Levels up to ～2MeV in excitation energy were studied with a resolution of ～13keV (FWHM) and spectroscopic strengths were extracted. The low-lying states in¹⁹³Ir have been interpreted in terms of both the Nilsson and the rotation-vibration models including Coriolis, particle-vibration and rotation-vibrational couplings. The previously assigned 3/2⁺ [402], 11/2^? [505], 1/2⁺[400] and 1/2⁺[411] bands were populated and candidates for the 5/2⁺ [402] and 7/2⁺ [404] bandheads were observed. TheK ₀ +2 gamma vibration based on the ground state was populated because it is mixed with the 7/2⁺ [404] state. Surprisingly, there was no significant difference between the stripping and pick-up strengths for the low-lying states in¹⁹³Ir, suggesting that the equilibrium nuclear shape of¹⁹³Ir has large overlaps with the shapes of both¹⁹²Os and¹⁹⁴Pt. The nuclear level structure of¹⁹⁵Ir appears to be similar to those of the lighter iridium isotopes.     

The nature of the high-voltage photo-emf in thin semiconductor layers

We have shown in [1] that in pyramidal crystals of semiconductors with linear dimensions of the order of a micron it is possible for a photodiffusion-emf of 0.025 V to arise.In this paper a mechanism of producing a high-voltage photo-emf in thin layers of semiconductors is proposed and discussed, the value of which considerably exceeds the width of the forbidden zone of the semiconductor in question, starting from the concept of the series connection of a large number of such elements. Despite the fact that this phenomenon was discovered quite long ago [2], its nature has not been finally cleared up.A photo-emf of 10 + 100 V over a 1-cm length of the film at room temperature is found in CdTe [2], Sb₂S₃, Sb₂Se₃ [3], Ge, Si [4, 5], PbS [6], GaAs [7], and ZnS [8].     

Optical and acoustic properties of 33PbIn1/2Nb1/2O3-35PbMg1/3Nb2/3O3-32PbTiO3 single crystals in an electric field

The influence of different conditions of applying a dc electric field (0 < E < 4 kV/cm) on the behavior of optical transmission and on the acoustic parameters (sound velocity and attenuation) in the [001]- and [011]-oriented single crystals 33Pb(In_1/2Nb_1/2)O₃-35PbMg_1/3Nb_2/3O₃-32PbTiO₃ existing near the morphotropic phase boundary has been investigated. It has been found that the optical transmission, sound velocity, and attenuation sharply change near the phase transition in a narrow range of electric fields for any method of their applying. In the field applied along [001], the change in the sound velocity due to the phase transition is 1.5 times greater than that in the field applied along [011]. This is caused by a larger contribution of the piezoelectric effect to the elastic modulus determining the sound velocity along [001] as compared to [011]. It has been shown that the number, symmetry, and stability of the phases formed in the field depend on the conditions of applying the field.     

Comparison of the ht Ultraviolet-Visible Spectra of the Copper(Ii) Complexes of Bidentate Schiff Base Ligands

Abstract

The bis(salicylaldiminato)copper(II) complexes of the ligand series of salicylaldimines derived from the condensation of n-alkyl or n-alkyloxy substituted aromatic amines with 2,4-dihydroxybenzaldehyde were synthesized. a series of Schiff base ligands with the general formula 4-X-N-(2,4-dihydroxybenzylidene)-aniline and differing only in substituents were synthesized. Some of these compounds have already been reported in literature. X=OCH₃[1],OC₂H₅[2],C₄H₉[1]. the copper(II) complexes of these ligands having the general formula, copper, bis[o-[N-(p-X-phenyl) formimidoyl]-4-hydroxyphenolato] were also synthesized. the ligands and their complexes, a total of 24 in number, are studied systematically with ultraviolet-visible spectroscopy to examine the effect of various n-alkyl- and n-alkyloxy substituents on the ligands and on their complexes. in the electronic spectrum of these compounds, the bands observed in the 200-450 run region which involve charge transfer π-π? transition were interpreted.     

Anomalous shift in crossing frequency for the proton 1/2[541] band in175Ta

High-spin states in¹⁷⁵Ta have been populated in the¹⁶⁰Gd (¹⁹F,4n)¹⁷⁵Ta reaction with beams provided by the HI-13 tandem accelerator at the Institute of Atomic Energy in Beijing. A level scheme was constructed from γ-γ coincidence experiments. Seven decay sequences built on 5/2⁺[402], 1/2^?[541], 7/2⁺[404] and 9/2^? [514] proton Nilsson configuration have been extended to higher spin. An anomalously large delay of the neutron AB crossing built on the h_9/2 proton Nilsson State 1/2^?[541] is discussed.     

Dielectric investigations in the nematic and hexatic smectic B phases of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl

Temperature-dependent dielectric characterization of 4-hexyl-4′-[2-(4-isothiocyanatophenyl)ethyl]-1,1′-biphenyl (HIEB), which exhibits smectic B and nematic phases, has been carried out over the frequency range of 1 Hz to 10 MHz for homeotropic and planar alignment of sample molecules. This compound shows positive dielectric anisotropy (Δε = ε _∥ ? ε _⊥ > 0) in the nematic (N) phase. One mode of dielectric relaxation showing Arrhenius behaviour has been detected in the hexatic smectic B (SmB) phase. Various electrical parameters, namely, dielectric anisotropy, relaxation frequency and activation energy, have been determined in the N and SmB phases.     

Modulated structure of the superconducting phases in Pb-modified Bi[sbnd]Sr[sbnd]Ca[sbnd]Cu[sbnd]O

Abstract

High resolution electron microscopy has shown that a modulated structure occurs in the Bi[sbnd]Sr[sbnd]Ca[sbnd]Cu[sbnd]O system. Electron diffraction and x-ray diffraction observations show that this modulation produces extra reflections. Diffraction patterns of the Pb-free material have superstructure reflections with wave vectors [0, 1/4.7, 1] and [0, ?1/4.7, 1]. These two waves vectors can generate all of the superstructure relections associated with each fundamental reflection. When PbO is added to the BSCCO system a new wave vector [0. 1/8.5, 0] is introduced. Observations show that within a single grain the two wave vectors coexist for a Pb and Bi ratio of about 0.25. This produces a non-uniform modulated structure which may be due to a superposition of the two wave vectors. The intensity of the [0, 1/4.7, 1] wave vector is substantially reduced in the Pb-modified material. The b' component of both wave vectors in incommensurate with the lattice period. The same superstructures occurs in both the low-T_c phase and the high-T_c phase.     

Thermal conductivity and heat capacity of Si3N4/BN fiber monoliths

This paper reports on measurements within the 5–300-K temperature interval of the thermal conductivity of Si₃N₄ and BN polycrystalline ceramic samples and Si₃N₄/BN fiber monoliths (FM) with different fiber arrangement architecture, [0], [90], and [0/90], with fibers arranged, accordingly, along and across the sample axis and the [0] and [90] layers stacked alternately. In the 3.5–300-K interval, the heat capacity at constant pressure, and at 77 K, the sound velocity have been measured in polycrystalline Si₃N₄ and BN samples and in Si₃N₄/BN [0] fiber monoliths. Our studies suggest that, with a high enough degree of confidence, but for some compositions—with minor assumptions, it can be maintained that, in the case of the Si₃N₄/BN fiber monoliths, one can use for calculation of their thermal conductivities and heat capacities within certain temperature intervals simple models considering mixtures of the Si₃N₄ and BN components with due account of their contributions to formation of the Si₃N₄/BN FM. It has been established that in the low-temperature domain (5–25 K), phonons in Si₃N₄/BN [0], [90], and [0/90] fiber monoliths scatter primarily from dislocations. This effect is not observed in ceramic Si₃N₄ and BN samples. The experimental data obtained on the thermal conductivity, heat capacity, and sound velocity have been used to calculate phonon mean free path lengths in polycrystalline Si₃N₄ and BN samples and the effective mean free path length in the Si₃N₄/BN [0] FM.     

High-resolution visible laser spectroscopy of HfF

The electronic spectrum of hafnium monofluoride has been investigated from 415 to 725 nm using a laser-ablation/molecular beam laser-induced fluorescence spectrometer. Several electronic systems were observed and data have been recorded at both low and high resolution. High resolution rotational analyses of the [17.4]1.5-X1.5 (0-0), [17.9]2.5-X1.5 (0-0), [19.7]0.5-X1.5 (0-0), [20.0]0.5-X1.5 (0-0), [21.1]2.5-X1.5 (0-0), [22.3]1.5-X1.5 (0-0), and [23.3]0.5-X1.5 (0-0) subbands have been carried out, resulting in accurate values for the ground and excited state effective rotational constants. Furthermore, the rotational analysis of the subbands assigned as [17.4]1.5-X1.5 (1-0) and [17.9]2.5-X1.5 (1-0) allows us to determine values of 589.7569(6) and 588.9076(6) cm⁻¹ for ΔG^′_1/2 [17.4] and ΔG^′_1/2 [17.9], respectively. From dispersed fluorescence data we find that ΔG^′′_1/2=670(13) cm⁻¹ for the ground state and that another low-lying electronic state lies at ∼2850 cm⁻¹. The data also suggests that a second low-lying electronic state lies at ∼5200 cm⁻¹ above the ground state.     

Spectroscopy of NdO: New results

¹⁴²NdO molecules have been produced by heating ¹⁴²Nd₂O₃ to about 2100 K in a vacuum furnace in the presence of argon gas. A ring dye laser operating with DCM dye has been used to excite ¹⁴²NdO transitions in the 636-666 nm spectral region, and induced fluorescence has been spectroscopically analysed at high resolution with a Fourier transform spectrometer. Contributions from thermal emission have been simultaneously observed. Two new low-lying electronic states have been detected, at energies of about 2708 and 4139 cm⁻¹, designated as [2.7], most probably observed at ν = 1, and [4.1], likely to be (2)6 (observed at ν = 0). The ν = 1 level of the (1)6 state, already known at ν = 0, has been observed for the first time. Most levels pumped by the laser, between 14 000 and 17 400 cm⁻¹, could be identified from earlier work. In addition, by studying in more detail recently obtained fluorescence spectra [J. Mol. Spectrosc. 225 (2004) 132] spectroscopic constants have been improved for a number of states. Finally, from thermal emission spectra, rotational analyses of the 0-0 bands of two new systems, [16.4] − (2)5 and [14.1] − X4, and reanalyses at higher resolution of the 0-0 bands of the systems V, VII, VIII, and X have been carried out. A consistent set of spectroscopic constants of the levels of ¹⁴²NdO characterized as yet is presented.     

超高泵浦功率下的Xe(6p[1/2]0, 6p[3/2]2, 和6p[5/2]2)原子的能量转移过程

本文研究了Xe(6p[1/2]₀, 6p[3/2]₂, and 6p[5/2]₂)原子在聚焦条件下的动力学过程. 激发能级的原子密度在聚焦条件下会显著地增加,因此两个高激发态原子之间的energy-pooling碰撞的概率也会增加. 这种energy-pooling碰撞主要有三种类型. 第一种类型为energy-pooling碰撞导致的电离. 一旦将激发激光聚焦,就可以从侧面的窗口观察到非常明显的电离现象,不论激发能级是6p[1/2]₀、6p[3/2]₂或6p[5/2]₂能级. 这种电离的产生机理是energy-pooling电离或者一个Xe^*原子再吸收一个光子产生电离. 第二种类型为跨越较大能极差的energy-pooling碰撞. 当激发能级为6p[1/2]₀能级的情况下,两个6p[1/2]₀原子碰撞会产生一个5d[3/2]₁原子和一个6s''[1/2]₀原子. 第三种类型为跨越较小能级差的energy-pooling碰撞. 以5个二次产生的6p能级为上能级的荧光强度都变得更强,并且这些荧光的上升沿都变得更陡峭. 产生这些6p原子的主要机理是energy-pooling碰撞并非简单的碰撞弛豫. 基于理想气体原子之间的碰撞概率公式,推导出两个6p[1/2]₀原子的energy-pooling碰撞速率为6.39x10⁸s^-1. 此外,6s原子在聚焦条件下的密度也会增加. 因此所有的荧光曲线会因为辐射俘获效应而出现非常严重的拖尾.     

Dynamics of mixed valent Europium and Samarium systems

For mixed valent Europium and Samarium systems dynamical magnetic and charge susceptibilities are calculated at temperatures above their fluctuation temperature using Mori's formalism. The low-lying spin-orbit excited level of the 4f ⁶ -configuration leads to additional relaxation modes and to conspicuous temperature effects.Dedicated to B. Mühlschlegel on the occasion of his 60th birthdayResearch performed within the program of the Sonderforschungsbereich 125 (Aachen-Jülich-Köln)Part of this work has been presented at the 2nd General Conference of the Condensed Matter Division of the EPS, Manchester (1982) [4], at the ICM '82, Kyoto [5], at the DPG spring meeting, Freudenstadt (1983) [6], and at the Nato ASI on Moment Formation in Solids, Vancouver Island (1983) [7]     

Rotational reorientation dynamics of Rhodamine 700 in different excited states

The rotational reorientation dynamics of rhodamine 700 (LD700) in the first (S₁) and the fifth (S₅) excited state in three aprotic polar solvents have been investigated using femtosecond time-resolved stimulated emission pumping fluorescence depletion (FS TR SEP TD) spectroscopy. In both excited states, the overall rotational relaxation of LD700 occurs on a time scale of 40-230 ps depending on the solvent, and a quantitative analysis of this time constant has been performed using the Stokes-Einstein-Debye (SED) hydrodynamic theory combined with the extended charge distribution model developed by Alavi and Waldeck. The experimentally measured reorientation times for LD700 in S₅ are smaller than those in S₁, which is in accord with the predictions by the SED theory. In addition, for LD700 in S₅, a rapid initial decrease on the time scale less than 0.5 ps has been found. According to our analysis, this fast component may account for the rapid internal conversion from S₅ to S₁, and the rate of internal conversion was found to be sensitive to the solvent polarity.     

Nuclear Spin-Lattice Relaxation of 82BrFe

The field dependence of the nuclear spin-lattice relaxation (SLR) of cold implanted ⁸²Br (T ≤ 25 mK) in α-Fe single crystals was investigated with nuclear magnetic resonance of oriented nuclei (NMR/ON) at low temperatures as experimental technique. The SLR at the lattice sites with the hyperfine fields found by earlier NMR/ON experiments was measured as a function of the applied external magnetic field B _ext parallel to the three principle axes [100], [110] and [111] of the iron single crystal. The data were evaluated with the full relaxation formalism in the single impurity limit and for comparison also with the often employed model of a single exponential function with an effective relaxation time T ₁′. With a phenomenological model the high field values of the relaxation rates r _{∞, [100]′} = 6.6(2) · 10⁻¹⁵ T²sK⁻¹, r _{∞, [110]} = 5.4(2) · 10⁻¹⁵ T²sK⁻¹ and r _{∞, [111]} = 5.2(1) · 10⁻¹⁵ T²sK⁻¹ were obtained.