Temperature Dependence for the Relative Raman Cross Section of the Ammonia/Water Complex

The Raman spectra of aqueous ammonia solutions have been obtained between -40 and 25 degrees C. The Raman spectrum of neat water was also obtained at 25 degrees C and is characterized by two broad peaks observed at 3200 and 3400 cm(-1). The spectrum due to water is subtracted to determine the NH(3) spectrum at all temperatures. In ammonia-water solutions, the spectrum shows three features at measured displacements of 3250, 3316, and 3400 cm(-1). The feature at 3316 cm(-1) is assigned to the Q branch of the symmetric stretch. The broad, weak features at 3250 and 3400 cm(-1), previously assigned to rotational bands, are assigned to combination bands. The NH(3) combination bands are assigned by comparing with sum frequency generation (SFG) experiments, monitoring changes with temperature, and analyzing the polarization data. The rotational structure of the Q band is also discussed. As the temperature is lowered from 25 to -40 degrees C, an increase in the Raman intensity is observed for all bands. The relative Raman scattering cross section is determined from the numerically integrated area of the NH(3) Q branch at each temperature. Copyright 2001 Academic Press.     

Molecular structure of polystyrene at Air/Polymer and Solid/Polymer interfaces

IR-visible sum-frequency generation (SFG) spectroscopy has been used in a total internal reflection geometry to study the molecular structure of polystyrene (PS) at PS/sapphire and PS/air interfaces, simultaneously. The symmetric vibrational modes of the phenyl rings dominate the SFG spectra at the PS/air interface as compared to the antisymmetric vibrational modes at the PS/sapphire interface. This indicates approximately parallel orientation of the phenyl rings at the PS/air interface while nearly perpendicular orientation at the PS/sapphire interface, with respect to the surface normal.     

Self-diffusion in a liquid complex plasma

Self-diffusion has been experimentally studied in a two-dimensional underdamped liquid complex (dusty) plasma. It was found that the self-diffusion coefficient D increases linearly with the temperature T: D/omega(E)a2 = (0.019 +/- 0.007)(T/T(m) - 1), where T(m), omega(E), and a are the melting temperature, the Einstein frequency, and the mean particle separation, respectively. No superdiffusion was observed, whereas a subdiffusion occurred at temperatures close to melting.     

Anomalous behavior of superconducting-normal mesoscopic structures near T(c)

We observe a maximum in the conductance of Al/n-GaAs junctions at temperatures 20 mK lower than the superconducting transition temperature (T(c)). This is the first observation of a peak in the conductance near the superconducting transition in superconducting-normal (S/N) junctions. To accommodate this effect we calculate the full temperature dependence of the conductance of these structures, invoking quasiclassical Green's functions in the diffusive limit. In addition to the well-known low-temperature peak at temperatures on the order of the Thouless energy, we find a maximum near T(c). This peak has the same origin as the subgap conductance observed in S/N junctions at low temperatures.     

Absolute Orientation of Molecules with Competing Hydrophilic Head Groups at the Air/Water Interface Probed with Sum Frequency Generation Vibrational Spectroscopy

和频振动光谱(SFG-VS)研究中由基团在界面上取向所引起的光谱增强或相消的干涉现象为研究分子在界面上的绝对取向提供了一种直接的测量方法. 这一方法比SFG实验中复杂的相位测量方法更为直接和简单可行. 以在空气/水界面取向已知的对羟基苯腈(PCP)分子的氰基(-CN)基团为相位参考来获得3,5-二甲基对羟基苯腈(35DMHBN)和2,6-二甲基对羟基苯腈(26DMHBN)分子在空气/水界面的取向信息. 通过对这三种分子的水溶液和它们两两混合溶液界面上-CN基团和频振动光谱强度的比较,发现在空气/水界面的3     

Spin-reorientation, ferroelectricity, and magnetodielectric effect in YFe(1-x)Mn(x)O3(0.1 ≤ x ≤ 0.40)

We report the observation of magnetoelectric and magnetodielectric effects at different temperatures in Mn-substituted yttrium orthoferrite, YFe(1-x)Mn(x)O(3)(0.1 ≤ x ≤ 0.40). Substitution of Mn in antiferromagnetic YFeO(3)(T(N) = 640 K) induces a first-order spin-reorientation transition at a temperature, T(SR), which increases with x whereas the Néel temperature (T(N)) decreases. While the magnetodielectric effect occurs at T(SR) and T(N), the ferroelectricity appears rather at low temperatures. The origin of magnetodielectric effect is attributed to spin-phonon coupling as evidenced from the temperature dependence of Raman phonon modes. The large magnetocapacitance (18% at 50 kOe) near T(SR) = 320 K and high ferroelectric transition temperature (～115 K) observed for x = 0.4 suggest routes to enhance magnetoelectric effect near room temperature for practical applications.     

Structure and melting of dipole clusters

Two-dimensional clusters of particles, repelling due to dipole-dipole interactions and confined by an external parabolic potential, are considered. The model describes different physical systems, particularly electrons in semiconductor structures, or electrons above a drop of He near a metal electrode, a drop of colloid liquid etc. Two kinds of ordering are in competition in the clusters: a triangular lattice and a shell structure. The ground-state configurations corresponding to the local and global minima of the potential energy for clusters with N = 1 – 40 “particles” are calculated. The structure, the potential energy and the radial and angular r.m.s. displacements as functions of temperature are also calculated. Analysing these quantities the melting of clusters is studied. One- or two-stage melting occurs depending on the number of particles in the cluster. In the case of clusters consisting of two shells melting has two stages: at lower temperature reorientation of neighbouring shells (“orientational melting”) arises; at much higher temperatures the radial shell order disappears. In clusters consisting of more than two shells total melting occurs as a first-order one-stage transition (analogously to a dipole crystal). This is connected with the barrier of rotation being less than the barrier of interchange of particles between shells for small microclusters while the barriers are of equal order for clusters with a greater number of particles.     

Atomistic simulation of slow grain boundary motion

Existing atomistic simulation techniques to study grain boundary motion are usually limited to either high velocities or temperatures and are difficult to compare to realistic experimental conditions. Here we introduce an adapted simulation method that can access boundary velocities in the experimental range and extract mobilities in the zero driving force limit at temperatures as low as ～0.2T(m) (T(m) is the melting point). The method reveals three mechanistic regimes of boundary mobility at zero net velocity depending on the system temperature.     

Molecular mobility and fracture processes in ultimately drawn high-density polyethylene

The reasons for cessation of drawing and for the local fracture processes occurring in linear polyethylene near ultimate draw ratios, λ_max, have been studied by broad-line proton NMR and scanning electron microscopy. As λ_max was reached during drawing, the sample whitened and kink bands similar to those observed at deformation of low molecular solids were formed. The kink bands were clearly seen in the micrographs. As evidenced by NMR, the segmental mobility of chains in the amorphous regions is almost completely suppressed because of a sharp increase of the orientation stress near λ_max (though the temperature of drawing is close to the melting temperature). This phenomenon of mechanical vitrification is regarded as a fundamental reason for cessation of drawing and for transition to the “solid-state” fracture mechanism. Quantitative estimates are given for formation of submicrocracks arising at boundaries of kink bands.     

Double-peak resistivity transport properties of La0.67Ca0.33MnO3 ceramics

Polycrystalline samples of La_0.67Ca_0.33MnO₃ were prepared by solid-state reactions by varying the pelletization force and the sintering temperature. Lowering the sintering temperature gave rise to smaller grains and increased the overall resistivity of the ceramic. Partial melting was observed in the ceramics sintered at higher temperatures (1400-1500 °C). Additionally, these ceramics showed two distinct resistivity peaks. The resistivity peak near the magnetic transition (T_C) was sharp, whereas the second peak was a broad one observed below T_C.     

Er1-xDyxNi2B2C体系中超导和磁性的共存和相互作用

本在2K～20K温区内系统地研究了Er1-xDyxNi2B2C体系中超导转变温度Tc的反铁磁转变温度TN随Dy掺杂含量x的变化．实验发现x=0．3和x=0．8附近的样品具有复杂的磁结构．这些洋品有两个磁转变温度(TN’和TN)．对于该体系发现了两个主要的特征：1)在x=0．3附近，超导被抑制，TN’出现一个小的峰值；2)在x=0．8附近，Tc出现一个低谷，TN’出现一个大的宽峰．TN’在x=0．3和x=0．8附近的异常来源于改系统中超导和磁性的共存和相互作用。     

Sum frequency generation (SFG) – surface vibrational spectroscopy studies of buried interfaces: catalytic reaction intermediates on transition metal crystal surfaces at high reactant pressures; polymer surface structures at the solid–gas and solid–liquid interfaces

SFG spectra of polyethylene and polypropylene show monolayer sensitivity and reveal temperature-dependent changes of surface structure. For polymer blends, the hydrophobic component segregates to the solid–air interface, and the hydrophilic component segregates at the solid–water interface. Changes in SFG spectra of polymer blends as a function of bulk concentration correlate with changes of contact angle. SFG is an excellent probe of surface-structure and surface-composition changes as the polymer interface is altered. Received: 20 September 1998     

Heteronuclear double resonance study of pentafluorobenzene

The electronic absorption spectrum of solid Würster's blue perchlorate in the low temperature phase was measured at various temperatures, special attention being paid to the first π* ← π transition band of the monomer at ～ 600 mμ. The isosbestic points were clearly found for the spectral curves measured at several different temperatures, showing the coexistence of two transition bands in this wavelength region. By analysing the temperature dependence of the absorption intensity and by comparing the result with E.S.R. data, these two bands were interpreted as the singlet-singlet and triplet-triplet absorption bands originating from the ground singlet state and the thermally accessible triplet state, respectively. A similar result was obtained for the 260 mμ band. The present results can be interpreted by the dimer model for the low temperature phase of Würster's blue perchlorate but are inconsistent with the disproportionation mechanism for the phase transition.

The singlet-singlet and triplet-triplet transition bands were separately obtained for each of the 600 mμ and 260 mμ bands from analysis of the temperature dependence; the singlet-triplet separation in the corresponding excited states is 310±80 cm^-1 and 530±200 cm^-1, respectively, with the triplet state at lower energy.     

Impact of intermolecular vibrational coupling effects on the sum-frequency generation spectra of the water/air interface

ABSTRACT

We have examined the impact of intermolecular vibrational coupling effects of the O-H stretch modes, as obtained by the surface-specific velocity-velocity correlation function approach, on the simulated sum-frequency generation spectra of the water/air interface. Our study shows that the inclusion of intermolecular coupling effects within the first three water layers, i.e. from the water/air interface up to a distance of 6?Å towards the bulk, is essential to reproduce the experimental SFG spectra. In particular, we find that these intermolecular vibrational contributions to the SFG spectra of the water/air interface are dominated by the coupling between the SFG active interfacial and SFG inactive bulk water molecules. Moreover, we find that most of the intermolecular vibrational contributions to the spectra originate from the coupling between double-donor water molecules only, whereas the remaining contributions originate mainly from the coupling between single-donor and double-donor water molecules.     

Optical behaviour of melting for a thin metal film

Reflectance measurements have been performed for gallium films at normal incidence (from 0.3 to 0.9 μm) in terms of temperature (from -20°C to + 40°C). The basic results are: (i) a drastic change in reflectance when melting occurs (about 20% at 0.6 μm), and (ii) a shift in the temperature of the solid-liquid transition with the thickness of the film which only takes place on and after the second melting (about 7°C for a film 250A?thick).     

Ion association in model ionic fluids

Monte Carlo simulations are used to investigate the temperature and pressure (density) dependence of ion association in the restricted primitive model. It is shown that at temperatures below the critical temperature T(c) the vapor consists almost exclusively of strongly bound ion pairs at or near contact. Significant ion-pair dissociation begins at temperatures very near T(c). This raises the possibility that compositional fluctuations between strongly bound and free ions influence the critical behavior. We note qualitative similarities between the present results and the Kosterlitz-Thouless transition in the two-dimensional Coulomb gas.     

空气/水界面水分子的取向和运动

对四种不同的实验构型下空气／水界面自由O-H键在3700cm~(-1)的和频振动光谱的分析表明,水分子在空气／水界面的取向运动只可能是在平衡位置附近有限角度之内的受限转动。界面水分子的自由O-H键取向距界面法线约33°,而取向分布或运动的宽度不超过15°。这一图像显著地不同于Wei等人(Phys. Rev. Lett.86,4799(2001))只通过单一的SFG实验构型所得出结论,即：空气／水界面的水分子在超快的振动弛豫时间内在很大的角度范围内运动。     

In Situ Transmission Electron Microscopy Observation of Melted Germanium Encapsulated in Multilayer Graphene

Germanene is a two-dimensional germanium (Ge) analogous of graphene, and its unique topological properties are expected to make it a material for next-generation electronics. However, no germanene electronic devices have yet been reported. One of the reasons for this is that germanene is easily oxidized in air due to its lack of chemical stability. Therefore, growing germanene at solid interfaces where it is not oxidized is one of the key steps for realizing electronic devices based on germanene. In this study, the behavior of Ge at the solid interface at high temperatures is observed by transmission electron microscopy (TEM). To achieve such in situ heating TEM observation, this work fabricates a graphene/Ge/graphene encapsulated structure. In situ heating TEM experiments reveal that Ge like droplets move and coalesce with other Ge droplets, indicating that Ge remains as a liquid phase between graphene layers at temperatures higher than the Ge melting point. It is also observed that Ge droplets incorporate the surrounding amorphous Ge as Ge nuclei, thereby increasing its size (domain growth). These results indicate that Ge crystals can be grown at the interface of van der Waals materials, which will be important for future germanene growth at solid interfaces.     

The effects of internal rotation on some infrared and electronic band contours of tetrolaldehyde

Contour calculations are reported for one electronic band and three infrared bands of tetrolaldehyde, CH₃CCCHO, where the methyl group executes relatively free internal rotation with respect to the body of the molecule. The electronic band described, the 0-0 band of the π^∗ ← n transition near 3760 Å, has the transition moment located in the molecular frame. The infrared bands are the 3 degenerate perpendicular bands of the methyl group, having the transition moments localized in the rotating group. Gross differences in contour are observed in the two types of bands.     

Effect of the alpha-gamma phase transition on the stability of dislocation loops in bcc iron

Body-centered-cubic iron develops an elastic instability, driven by spin fluctuations, near the alpha-gamma phase transition temperature T(c) = 912 degrees C that is associated with the dramatic reduction of the shear stiffness constant c' (c(11)-c(12))/2 near T(c). This reduction of c' has a profound effect on the temperature dependence of the anisotropic elastic self-energies of dislocations in iron. It also affects the relative stability of the a[100] and a/2[111] prismatic edge dislocation loops formed during irradiation. The difference between the anisotropic elastic free energies provides the fundamental explanation for the observed dominant occurrence of the a[100], as opposed to the a/2[111], Burgers vector configurations of prismatic dislocation loops in iron and iron-based alloys at high temperatures.