Investigation of inverse Raman scattering using the method of intra-cavity spectroscopy

The detectability of Raman absorption lines is enhanced by inserting the Raman sample into the cavity of a broad-band dye laser where the sample is simultaneously pumped by monochromatic radiation. With this technique we were able to detect Raman samples with good scattering efficiencies in a concention of 10^?3 mole/? or to obtain nearly complete Raman spectra within a time interval of 30 nsec.Exposures in which the dye laser radiation and the strong monochromatic radiation are polarized parallel or perpendicularly to each other are compared with spontaneous Raman spectra which are polarized parallel or perpendicularly.     

Diagnostics of skin pathologies based on spectral analysis of backward and raman scattering

A mathematical model of the interaction of optical radiation with skin tissues is developed taking into account stimulated Raman scattering. Numerical experiments show that the backscattering spectra possess specific features typical of skin pathologies. It is shown that the pathology type can be determined from an analysis of the differential ratios of the Raman scattering intensities at 1271 and 1663 cm^?1 to the intensity in the region of 1454 cm^?1. It is found that the difference in the differential ratios of the Raman scattering intensities for pathologically changed and normal layers may exceed 40%.     

Experimental and numerical investigation of microscale hydrogen diffusion flames

Characteristics of microscale hydrogen diffusion flames produced from sub-millimeter diameter (d = 0.2 and 0.48 mm) tubes are investigated using non-intrusive UV Raman scattering coupled with LIPF technique. Simultaneous, temporally and spatially resolved point measurements of temperature, major species concentrations (O₂, N₂, H₂O, and H₂), and absolute hydroxyl radical concentration (OH) are made in the microflames for the first time. The probe volume is 0.02 × 0.04 × 0.04 mm³. In addition, photographs and 2-D OH imaging techniques are employed to illustrate the flame shapes and reaction zones. Several important features are identified from the detailed measurements of microflames. Qualitative 2-D OH imaging indicates that a spherical flame is formed with a radius of about 1 mm as the tube diameter is reduced to 0.2 mm. Raman/LIPF measurements show that the coupled effect of ambient air leakage and pre-heating enhanced thermal diffusion of H₂ leads to lean-burn conditions for the flame. The calculated characteristic features and properties indicate that the buoyancy effect is minor while the flames are in the convection–diffusion controlled regime because of low Peclet number. Also, the effect of Peclet number on the flame shape is minor as the flame is in the convection–diffusion controlled regime. Comparisons between the predicted and measured data indicate that the trends of temperature, major species, and OH distributions are properly modeled. However, the code does not properly predict the air entrainment and pre-heating enhanced thermal-diffusive effects. Therefore, thermal diffusion for light species and different combustion models might need to be considered in the simulation of microflame structure.     

Thermal loss mechanism in the generation of multifrequency laser emission via stimulated Raman scattering and four-wave Raman mixing studied by photothermal refraction spectroscopy

The heat produced in conjunction with the processes of stimulated Raman scattering and four-wave Raman mixing in hydrogen was measured by photothermal refraction spectroscopy. Many vibrational, rotational, and vibrationally shifted rotational Raman lines are exclusively/simultaneously generated by changing the polarization of the laser beam and the hydrogen pressure. Thermal loss occurs predominantly from vibrational Raman scattering, which can be ascribed to a large Raman shift frequency of 4155 cm^-1 for the vibrational transition. In contrast to stimulated Raman scattering, little or no thermal loss is observable during the process of four-wave Raman mixing. Received: 12 April 1999 / Revised version: 12 July 1999 / Published online: 20 October 1999     

Determination of Very Slow Diffusion of Paramagnetic Ions by NMR Spectroscopy

In this paper, we propose a new method of measuring the very slow paramagnetic ion diffusion coefficient using a commercial high-resolution spectrometer. If there are distinct paramagnetic ions influencing the hydrogen nuclear magnetic relaxation time differently, their diffusion coefficients can be measured separately. A cylindrical phantom filled with Fricke xylenol gel solution and irradiated with gamma rays was used to validate the method. The Fricke xylenol gel solution was prepared with 270 Bloom porcine gelatin, the phantom was irradiated with gamma rays originated from a ⁶⁰Co source and a high-resolution 200 MHz nuclear magnetic resonance (NMR) spectrometer was used to obtain the phantom ¹H profile in the presence of a linear magnetic field gradient. By observing the temporal evolution of the phantom NMR profile, an apparent ferric ion diffusion coefficient of 0.50 μm²/ms due to ferric ions diffusion was obtained. In any medical process where the ionizing radiation is used, the dose planning and the dose delivery are the key elements for the patient safety and success of treatment. These points become even more important in modern conformal radio therapy techniques, such as stereotactic radiosurgery, where the delivered dose in a single session of treatment can be an order of magnitude higher than the regular doses of radiotherapy. Several methods have been proposed to obtain the three-dimensional (3-D) dose distribution. Recently, we proposed an alternative method for the 3-D radiation dose mapping, where the ionizing radiation modifies the local relative concentration of Fe²⁺/Fe³⁺ in a phantom containing Fricke gel and this variation is associated to the MR image intensity. The smearing of the intensity gradient is proportional to the diffusion coefficient of the Fe³⁺ and Fe²⁺ in the phantom. There are several methods for measurement of the ionic diffusion using NMR, however, they are applicable when the diffusion is not very slow.     

First-principles investigation of diffusion behaviours of H isotopes:From W(110) surface into bulk and in bulk W

<正>The diffusion behaviours of hydrogen（H）,deuterium（D）,and tritium（T） from W（110） surface into bulk and in bulk W are investigated using first-principles calculations combined with simplified models.The diffusion energy barrier is shown to be 1.87 eV from W（110） surface to the subsurface,along with a much reduced barrier of 0.06 eV for the reverse diffusion process.After H enters into the bulk,its diffusion energy barrier with quantum correction is 0.19 eV. In terms of the diffusion theory presented by Wert and Zener,the diffusion pre-exponential factor of H is calculated to be 1.57×10^-7 m²·s^-1,and it is quantitatively in agreement with the experimental value of 4.1×10^-7 m²·s^-1. Subsequently,according to mass dependence(（1/m）^1/2) of H isotope effect,the diffusion pre-exponential factors of D and T are estimated to be 1.11×10^-7 m²·s^-1 and 0.91×10^-7 m²·s^-1,respectively.     

Sonochemical activity in ultrasonic reactors under heterogeneous conditions

Due to its physical and chemical effects, ultrasound is widely used for industrial purposes, especially in heterogeneous medium. Nevertheless, this heterogeneity can influence the ultrasonic activity. In this study, the effect of the addition of inert glass beads on the sonochemical activity inside an ultrasonic reactor is investigated by monitoring the formation rate of triiodide, and the ultrasonic power is measured by calorimetry and by acoustic radiation. It was found that the sonochemical activity strongly depends on the surface area of the glass beads in the medium: it decreases above a critical area value (around 10⁻² m²), partly due to wave scattering and attenuation. This result is confirmed for a large range of frequencies (from 20 to 1135 kHz) and glass beads diameters (from 8-12 µm to 6 mm). It was also demonstrated that above a given threshold of the surface area, only part of the supplied ultrasonic power is devoted to chemical effects of ultrasound. Finally, the acoustic radiation power appears to describe the influence of solids on sonochemical activity, contrary to the calorimetric power.     

基于铜网置换反应的微纳结构SERS基底制备和应用

电力能源发展与国家经济发展关系密切,因此电网稳定、安全地运行是人民稳定生活的保障。而与稳定可靠的电网的运行有关的是变压器的绝缘水平,因此始终注意电气设备的状况和运行非常重要。而仅由纸绝缘产生的糠醛是目前用于评估电力变压器老化状况最常用的指标之一,所以准确测量变压器油中糠醛含量具有重大意义。拉曼光谱法可以实现对待测物的快速、无损检测,但受限于拉曼散射信号弱,对油中老化特征物这种微量物质检测难度大。表面增强拉曼光谱可以解决痕量物质检测的灵敏性问题,使溶解在变压器油中的老化特征物得到快速、无损地检测。故将SERS应用到变压器油中糠醛的检测对于变压器运行状况的评估具有重要的意义。围绕着变压器油中糠醛作为痕量物质检测灵敏度低的问题,基于置换反应在TEM铜网上制备了微纳米结构的SERS基底,以检测变压器油中的糠醛,为高效,准确地检测变压器油的老化水平提供一种快速、有效的新技术。选择了特定的实验材料,在控制特定的实验条件下基于置换反应制备出微纳结构SERS基底,经过电镜扫描对其表面形貌进行表征;在不同位置进行拉曼检测得到特征拉曼峰峰强的变异系数仅为3.55％,表明该基底的“热点”分布均匀和检测可重复性高;定性分析了一定浓度梯度的变压器油中糠醛和背景噪声的拉曼光谱。选择了1 702 cm-1的拉曼峰作为油中糠醛的特征拉曼峰。定量分析中,建立内标峰和1 702 cm-1处峰强比与变压器油中糠醛浓度的线性函数,得到良好的线性关系。使用3δ准则计算变压器油中糠醛在微纳结构SERS基底上的检测下限约为0.51 mg·L-1。研究说明基于铜网置换反应的微纳结构SERS基底对于变压器油中糠醛具有更灵敏的检测。这对于诊断电力变压器绝缘状况和维护电网稳定非常重要。     

Laser optoacoustic measurement of paper porosity

The propagation of broadband ultrasonic pulses in combined media that consist of printing paper of different porosity saturated with different liquids is studied. The experiments are performed with three types of paper, namely, Zoom Ultra (Stora Enso, Finland) with surface densities of 80 and 100 g/m² and Data Copy (Mo Do, Sweden) with a surface density of 160 g/cm², and with two types of saturating liquids: ethanol and transformer oil. To excite ultrasonic pulses and to detect them with a high time resolution, the laser optoacoustic spectroscopy method is used. For each type of liquid-saturated paper, the phase velocity of ultrasound is measured in the frequency range of 5–35 MHz. The absence of any noticeable frequency dispersion of the phase velocity is revealed. The possibility of measuring the porosity of printing paper on the basis of the theoretical model of a two-phase medium with the use of the corresponding experimental data is demonstrated.     

Diffusion of hydrogen in metals

The present status of our understanding of the diffusion of hydrogen in metals, both experimental and theoretical, is reviewed. Discussions are focused on the mechanism of diffusion of hydrogen isotopes H, D and T in f.c.c. and b.c.c. metals; the positive muon (μ ⁺) is referred to where appropriate. An up-to-date compilation of diffusion data as a function of temperature and isotope mass has been made, and a clear distinction in general diffusion behaviour in f.c.c. and b.c.c. metals is noted. Subsequently, the results obtained from the Gorsky effect, nuclear magnetic resonance and quasi-elastic neutron scattering that provide information on elementary jump processes are discussed.

A conceptual framework of the quantum diffusion of light interstitials in metals is given, including the recent Kondo theory that emphasizes the crucial importance of particle-conduction electron interactions in the diffusion process, especially at low temperatures. It is shown with the help of recent estimates of the tunneling matrix element that the overall feature of diffusion of hydrogen isotopes in b.c.c. metals as well as μ ⁺ in f.c.c. metals can be explained consistently within the frame presented here.

Finally, recent advances in the diffusion studies on hydrogen in b.c.c. metals are described. They include a re-analysis of quench-recovery experiments that manifested nearly athermal diffusion of H, D and T in Ta at low temperatures, and an enormous enhancement of the diffusivity under stress (superdiffusion) observed for H and D in V.     

Determination of the lattice vibrations of imidazole by neutron scattering

The external molecular vibrations of deuterated imidazole have been investigated at 12 K for wave vectors along the three principal directions of the Brillouin zone by neutron scattering and by Raman scattering at the zone center. A complete symmetry assignment is obtained. The dominant role of the N-H … N hydrogen bond within the intermolecular interactions is reflected in a relatively simple manner in the shape of the dispersion curves because of the chain-like arrangement of hydrogen bonds. The experiment yields directly a stretching force constant of 0.33 mdyn Å^?1 for this bond. This value is compatible with monopole-dipole and dipole-dipole interactions as major contributions to the attractive interactions of the hydrogen bond of this length (2.86 Å). Relatively strong static monopoles and dipoles are confirmed by a $\text{CNDO}\text{2}$ calculation and are consequently incorporated into the interaction model.     

Antiresonance of Raman Scattering in CdSxSe1-x Mixed Crystals

Abstract

Resonant enhancement of the Raman scattering cross section in II - IV semiconductors has recently received much attention both theoretically and experimentally. All existing theories anticipate a monotonic increase in the scattering intensities when the scattering radiation energy approaches the direct-energy gap. Contrary to them in an early Raman study of CdS¹ a cancellation of scattering efficiencies for the two TO modes prior to the onset of the resonance was pointed out. In a latter work on pure CdS Damen et al.² found even a more pronounced “antiresonance” behavior of the nonpolar E₂ phonon at 41 cm^?1. Thus, this striking feature seems to be rather common for the Raman active modes in CdS for which no electrooptic contribution to the scattering amplitude exists. The experimental data were qualitatively explained by assuming a destructive addition between nonresonant and the weaker resonant terms in LoudoN′s expression for the first-order Raman tensor³. Consequently the cancellation energy difference /E_G - hw_L/ depends on the ratio of the resonant term to the nonresonant terms.     

Raman scattering and luminescence of yttria nanopowders and ceramics

We have studied Raman scattering in yttria nanopowders and ceramics that was excited by radiation at wavelengths of 514.5 and 632.8 nm. We show that, in undoped nanopowders and cubic phase of doped yttria ceramics, only the Raman scattering by phonons is observed, with no other Raman scattering centers having been revealed. In nanopowders of the monoclinic phase, we have observed an additional Raman line with a Raman shift of 1093 ± 4 cm^?1. If all the objects under investigation are excited by the radiation at a wavelength of 514.5 nm, their spectra exhibit four series of photoluminescence lines, two of which (at λ = 521–523 and 538–564 nm) are emitted by Er³⁺ ions, “impurity” dopants, while the other two lines (at λ = 607–635 and 644–684 nm) are emitted by intrinsic centers. Under excitation by the radiation at a wavelength of 632.8 nm, only a series of bands at λ = 644–684 nm is emitted. In addition to these photoluminescence bands, neodymium-doped ceramics show photoluminescence bands of Nd³⁺ ions. We have shown that intrinsic luminescence centers, which occur in all the examined specimens, are capable of acting as acceptors with respect to neodymium ions excited to the upper laser level.     

Raman scattering in the submicrometer diamond membrane formed by the lift-off technique

Spectral characteristics of spontaneous Raman scattering in the submicrometer diamond membrane grown by the hydrogen implantation method are studied in comparison with the single-crystal diamond matrix. A shift in the main line of diamond one-photon excitation (sp ³-hybridization) at a frequency of 1324 cm^?1 is revealed in the diamond membrane. This fact indicates multiple internal strains (residual compression strains) due to residual defects and is a concequence of the use of the hydrogen implantation method (hydrogen is implanted into diamond to form a sacrificial layer.     

Lyman transitions of high rovibrationally excited H2, HD and D2 molecules

Energies and probabilities of Lyman transitions of high rovibrationally excited H₂, HD and D₂ molecules have been measured and compared with calculations. The experimental results are obtained from laser-induced fluorescence spectra that have been recorded in the spectral range from 60 500 to 83 500 cm⁻¹, covering 2/3 of the hydrogen Lyman band system. The necessary vacuum-UV radiation is produced by stimulated anti-Stokes Raman scattering, providing a widely tunable radiation source with narrow spectral bandwidth to resolve single Lyman transitions. The highest internal energies of detected hydrogen isotopologues are close to the dissociation limit. This extends the available data base of Lyman transitions from and to higher rotational states (J > 10) of HD and D₂.     

The temperature dependence of intensity and the function of the transition dipole moment for the induced optical absorption bands of oxygen in the region of the Herzberg photodissociation continuum (200–230 nm)

Application of coherent interaction of laser light with a focused ultrasonic wave to the technique of acoustooptic visualization in multiple-scattering media is discussed. By analyzing spatial distribution of the optical radiation modulated by ultrasound (the photocurrent at ultrasonic frequency), images of large-sized inhomogeneities embedded into the scattering medium have been obtained. A light-absorbing half-plane and a square with sides of 5 mm were used as the inhomogeneities. The visualization was performed under optimal conditions for measuring the alternating photocurrent calculated for the proposed model of coherent interaction between the laser and acoustic beams (the Raman-Nath diffraction). The alternating current at the ultrasonic frequency was obtained as a result of mixing the waves of the diffraction fields on the detector’s photocathode. All experimental values were obtained from a single measurement without averaging the alternating photocurrent at the ultrasonic frequency of 3 MHz, with the scattering parameter varying up to μL≤37.5, where μ is the extinction coefficient and L is the thickness of the scattering medium along the laser beam axis. The measured quantities varied in the course of the measurements by more than 10 orders of magnitude.     

Measurement of diffusion process of iron atoms under high pressure of hydrogen by time-domain analysis of nuclear resonant scattering of X-rays

We applied the time-domain analysis of nuclear resonant scattering (NRS) of X-rays for the study of the hydrogen-induced enhancement of atomic diffusion. The time-domain analysis of NRS is a powerful technique for studying diffusion processes on an atomic scale. The NRS measurement combined with high-pressure technique enables the direct measurement of self-diffusion processes under high hydrogen pressures. In this preliminary experiment, self-diffusion in 4 μm thick ⁵⁷Fe foils at 0.8 GPa was investigated. The samples of the ⁵⁷Fe were encapsulated with MgO or NaCl. Faster decays caused by diffusion of Fe atoms were observed in the time spectra of NRS at high temperatures. This enhancement of diffusion is believed to be the hydrogen-induced effect. In the present experiment, hydrogen should have been supplied to the samples by reaction with water originally adsorbed on NaCl/MgO powder particles. It was concluded that the diffusion of ⁵⁷Fe atoms under high pressure can be studied by nuclear resonant scattering of X-rays using a compact cubic-anvil press. The NRS method can also be extended to the study of atomic diffusion in the subsurface region by doping ⁵⁷Fe layer(s) at known depths.     

Giant enhancement of the Raman scattering by local magnon modes in FeF2:Mn2+

A study of the local magnon mode in FeF₂ crystals with Mn²⁺ impurities by inelastic Raman light scattering is presented. Though the interaction between the radiation and the Mn spins is negligible the scattering by the s₀ local mode is very strong. The data of the frequency and the scattering intensity are analyzed in terms of a magnetization coupled mode approach.     

Microwave diagnostics of ultracold neutral plasma

The microwave method is suggested to diagnose the ultracold neutral plasma. Based on the calculations of the dipole radiation, we derive the microwave scattering cross section of the ultracold neutral plasma, and microwave power scattered by the ultracold plasma is calculated as a function of time. The scattering cross section is nearly ¹⁰−11 m².     

Generation of multi-color stimulated raman emission from two-color linearly or circularly polarized pump beams

A laser beam at two different frequencies separated by 587 cm^–1 is focused into pressurized hydrogen (rotational transition energy, 587 cm^–1) to generate multi-color stimulated Raman emission. The polarization state and the pulse energy are measured for each generated emission line using linearly and circularly polarized pump beams. The effect of the polarization is discussed by using a parameter characterizing the polarizability of hydrogen and a conservation rule for the angular momentum in four-wave mixing. Many rotational lines are generated with linearly polarized pump beams through a four-wave mixing process. This is in striking contrast to the results obtained by using a single-color circularly polarized pump beam which generates only one rotational line through a conventional stimulated Raman process.