Theory of Raman light scattering by nanocrystal acoustic vibrations

A theory of Raman scattering of light by acoustic phonons in spherical nanocrystals of zinc-blende and wurtzite semiconductors has been developed with the inclusion of the complex structure of the valence band. The deformation-potential approximation was used to describe the exciton-phonon interaction. It is shown that this approximation allows only Raman scattering processes involving spheroidal acoustic phonons with a total angular momentum F=0 or 2. The effect of phonon quantum confinement on linewidth in Raman scattering spectra and scattered polarization is analyzed. An expression for the shape of the spectral line corresponding to nonresonant scattering from F=0 phonons was obtained. Fiz. Tverd. Tela (St. Petersburg) 41, 1473–1483 (August 1999)     

Scattering theory of one and two-photon molecular processes

Using a perturbation expansion of the transition operator T, a scattering theory of one and two-photon processes is developed. Distinction is made between Franck-Condon and Herzberg-Teller effects. The influence of each effect is analysed for vibrational and electronic absorption and finally for Raman scattering.     

Low frequency Raman scattering of anatase titanium dioxide nanocrystals

TiO₂ nanoparticle of size 7.8 nm are synthesized by wet chemical route and characterized by low-frequency Raman scattering (LFRS), transmission electron microscopy (TEM) and X-ray diffraction. The low frequency peaks in the Raman spectra have been explained using the Lamb's theory that predicts the vibrational frequencies of a homogeneous elastic body of spherical shape. Our results show that the observed low-frequency Raman scattering originates from the spherical (l=0) and quadrupolar vibrations (l=2) of the spheriodal mode due to the confinement of acoustic vibrations in TiO₂ nanoparticles. In addition to the low-frequency peak due to the vibrational quadrupolar and spheriodal modes, a band is also observed, which is assigned to the Raman forbidden torsional l=2 mode originating from the near spherical shape of the TiO₂ nanoparticles. The size distribution is also obtained from LFRS, which is in good agreement with TEM.     

Direct observation of p,p′‐dimercaptoazobenzene produced from p‐aminothiophenol and p‐nitrothiophenol on Cu2O nanoparticles by surface‐enhanced Raman spectroscopy

Surface‐enhanced Raman scattering of p‐aminothiophenol and p‐nitrothiophenol were obtained on the surface of Cu₂O nanoparticles, showing novel spectral changes with morphology‐dependent and time‐dependent characteristics. The measured Raman signals were believed to partly originate from the newly produced surface species p,p′‐dimercaptoazobenzene. The nature of surface chemisorption status during Raman measurement was investigated experimentally and theoretically via combined surface‐enhanced Raman scattering and density functional theory study, indicating that surface catalytic reaction of p‐aminothiophenol and p‐nitrothiophenol could take place on the surface of oxide nanostructures as well as coinage metal material. Copyright © 2013 John Wiley & Sons, Ltd.     

Surface-enhanced Raman scattering spectroscopic analysis of Saposhnikovia divaricata decoction

ABSTRACT

Surface-enhanced Raman scattering spectroscopy was employed to analyze the biochemical composition of the Saposhnikovia divaricata decoction, which is a common traditional Chinese medicine. No reliable Raman peak was observed in traditional Raman spectra of Saposhnikovia divaricata decoction. However, 12 main Raman peaks (534, 616, 648, 685, 730, 781, 850, 958, 1242, 1319, 1460, and 1571 cm^?1) were observed in the surface-enhanced Raman scattering spectroscopy spectra from the mixture of silver colloids with Saposhnikovia divaricata decoction as a result of the silver colloid enhanced effects on the Raman scattering of Saposhnikovia divaricata decoction. The results demonstrated that the surface-enhanced Raman scattering spectroscopy may provide a new kind of non-destructive, accurate, direct, and fast detecting method for the Saposhnikovia divaricata decoction or other traditional Chinese medicine in the form of decoction.     

The Raman effect in crystals

A review is given of progress in the theoretical and experimental study of the Raman effect in crystals during the past ten years. Attention is given to the theory of those properties of long-wavelength lattice vibrations in both cubic and uniaxial crystals which can be studied by Raman scattering. In particular the phenomena observed in the Raman scattering from crystals which lack a centre of inversion are related to the theory. The angular variations of the scattering by any type of lattice vibration in a crystal having any symmetry can be easily calculated using a complete tabulation of the Raman tensor. Recent measurements of first-order lattice vibration spectra are listed. A discussion of Brillouin scattering is included. The relation of second-order Raman spectra to critical points in the lattice vibration density of states is discussed, and measurements of the second-order spectra of diamond and the alkali halides are reviewed.

The theory and experimental results for Raman scattering by electronic levels of ions in crystals are examined, and proposals for Raman scattering by spin waves, electronic excitations across the superconductive gap and by plasmons are collected together.

Finally, the prospects for applying lasers as sources for Raman spectroscopy are discussed, and progress in the new technique of stimulated Raman scattering is reviewed.     

Non‐degenerate second‐order scattering and difference combination bands in infrared‐pump/anti‐Stokes resonance Raman‐probe experiments

Non‐degenerate second‐order scattering due to interaction of infrared and ultraviolet pulses is observed in picosecond infrared‐pump/anti‐Stokes Raman‐probe experiments under electronic resonance conditions. We detected resonance hyper‐Rayleigh scattering at the sum frequency of the pulses as well as the corresponding frequency‐down‐shifted resonance hyper‐Raman lines. Nearly coinciding resonance hyper‐Raman and one‐photon resonance Raman spectra indicate conditions of A‐term resonance Raman scattering. Second‐order scattering is distinguished from transient anti‐Stokes Raman scattering of v = 1 to v = 0 transitions and v = 1 to v′ = 1 combination transitions by taking into account their different spectral and temporal behaviour. Separating these processes is essential for a proper analysis of transient vibrational populations. Copyright © 2007 John Wiley & Sons, Ltd.     

Nonlinearity in Intensity versus Concentration Dependence for the Deep UV Resonance Raman Spectra of Toluene and Heptane

Abstract: The relation between Raman scattering, resonance Raman scattering, and absorption is reviewed to determine to what extent quantitative analysis can be applied in resonance Raman spectroscopy. In addition, it is demonstrated experimentally that normal Raman spectra can be dramatically inhibited by absorption and resonance Raman effects. Raman spectra of toluene and heptane mixtures—with progressively increasing concentrations of heptane—were measured using 229-nm laser excitation. The results show that the characteristic band intensities are not directly proportional to the relative concentrations of the compounds and deviate due to absorption resonance effects. An approximated mathematical model is developed to demonstrate that the intensities of the normal Raman scattering bands are suppressed. An inhibition coefficient K_i is introduced to describe the situation and determine the penetration depth. Most remarkably, it is shown that the intensity of the resonance Raman scattering bands can be constant even when the concentration ratios differ substantially in the sampled mixtures.     

Raman effect in the x-ray region

This paper presents a brief review of x-ray Raman scattering and some of our calculations on Raman scattered line shapes from light elements. We summarise the history of the Raman process in the x-ray region and present a detailed theory of the Raman scattering from an atomic many-electron system. Actual calculations of the Raman cross-section using this theory in single-particle approximation are given. The process of internal resonance Raman scattering is also discussed in the same formulation. The Raman cross-section is compared with the cross-sections of other x-ray scattering processes.     

Raman and Rayleigh spectroscopy and molecular motions

Raman and Rayleigh scattering experiments on HCl, DCl, HBr and DBr molecules (pure liquid or isotopically diluted) have been carried out at room temperature. Results are discussed in the light of the existing theories on molecular motions in the liquid phase. The comparison of Rayleigh and Raman scattering results shows that reorientational processes are not sufficient to explain completely the profile of anisotropic Raman scattering. According to a recent theory due to Bratos, the rotational correlation function can be obtained only after elimination of the vibrational correlation function determined from the isotropic Raman scattering. In this last case broadening may arise from three causes: translational motion, resonance broadening and vibration-rotation coupling. A comparative study of the band profile of anisotropic Rayleigh and Raman scattering shows that the wings in both cases come from essentially the same origin while a band moment analysis is consistent with Gordon's theory according to which they are of reorientational origin.     

Light scattering,flow birefringence and generalized hydrodynamics

The stress-optical coefficient ?, which is measured in flow birefringence experiments, is calculated using the generalized hydrodynamic equations which have been recently used to explain the k-dependent fine structure observed in depolarized (VH) light scattering. The resulting expressions allow a comparison of the strength of the birefiringence effect with that of the light scattering fine structure effect in a given liquid. It is seen that the combination of flow birefringence and VH scattering measurements yields the orientational structure factor g ⁽²⁾ of Ben-Reuven and Gershon. The theory is in reasonable agreement with experiment. The combination of our results with those of Raman and Krishnan yields a simple expression for the parameter δ which measures the strength of the stress-orientational effect. The dependence of the stress-optimal coefficient upon orientational order is briefly discussed.     

Frequency shifts in stimulated Raman scattering

The nonresonant contributions to the nonlinear susceptibility χ⁽³⁾ produce a frequency chirp during stimulated Raman scattering. In the case of transient stimulated Raman scattering, the spectrum of the generated Stokes pulse is found at higher frequencies than expected from spontaneous Raman data. The frequency difference can be calculated from the theory of stimulated Raman scattering.     

The Raman effect in crystals

A review is given of progress in the theoretical and experimental study of the Raman effect in crystals during the past ten years. Attention is given to the theory of those properties of long-wavelength lattice vibrations in both cubic and uniaxial crystals which can be studied by Raman scattering. In particular the phenomena observed in the Raman scattering from crystals which lack a centre of inversion are related to the theory. The angular variations of the scattering by any type of lattice vibration in a crystal having any symmetry can be easily calculated using a complete tabulation of the Raman tensor. Recent measurements of first-order lattice vibration spectra are listed. A discussion of Brillouin scattering is included. The relation of second-order Raman spectra to critical points in the lattice vibration density of states is discussed, and measurements of the second-order spectra of diamond and the alkali halides are reviewed. The theory and experimental results for Raman scattering by electronic levels of ions in crystals are examined, and proposals for Raman scattering by spin waves, electronic excitations across the superconductive gap and by plasmons are collected together. Finally, the prospects for applying lasers as sources for Raman spectroscopy are discussed, and progress in the new technique of stimulated Raman scattering is reviewed.     

Interband transitions and electronic Raman continuum in systems with strong inelastic scattering: Applications to YBa2Cu3O7-δ

We consider a model for the electronic Raman continuum which takes into account strong inelastic scattering and interband transitions. Calculations are based on four-vertex Raman scattering diagrams (Kawabata formalism) within the RPA for Coulomb interaction and the ladder diagram Bethe-Salpeter equation for the vertex. We apply this method to an analysis of the nature of the electronic Raman continuum in the normal state of the high-T _c superconductor YBa₂Cu₃O₇. In numerical calculations we take into account all the self-energy effects and make simulations for vertex corrections assuming that inelastic scattering is due to electron-phonon interaction. Theab-plane polarized continuum contains a large contribution from interband processes and does not depend strongly on temperature and inelastic scattering strength. The in-plane anisotropy is determined by interband transitions rather than by anisotropy of the Fermi surface. The ZZ continuum contains only weak contribution from interband transitions. It can be crudely described within a single band model with inelastic scattering and is strongly dependent on the relaxation rates of inelastic scattering. The nature of the oxygen-deficiency dependence of the Raman spectra is also commented upon.     

Multiphonon resonant Raman scattering in N‐doped ZnO

Multiphonon resonant Raman scattering in N‐doped ZnO films was studied, and an enhancement of the resonant Raman scattering process as well as longitudinal optical (LO) phonon overtones up to the sixth order were observed at room temperature. The resonant Raman scattering intensity of the 1LO phonon in N‐doped ZnO appears three times as strong as that of undoped ZnO, which mainly arises from the defect‐induced Raman scattering caused by N‐doping. The nature of the 1LO phonon at 578 cm⁻¹ is interpreted as a quasimode with mixed A₁ and E₁ symmetry because of the defects formed in the ZnO lattice. In addition, the previously neglected impurity‐induced two‐LO‐phonon scattering process was clearly observed in N‐doped ZnO. Copyright © 2009 John Wiley & Sons, Ltd.     

Vibrational spectroscopy of a compound with a CS7 ring

The product of the Asinger reaction between elemental sulfur, n‐butylamine and acetophenone is 8‐(n‐butylaminophenylmethyliden)‐1,2,3,4,5,6,7‐heptathiocane which contains a CS₇ ring. A combination of infrared, Raman and inelastic neutron scattering spectroscopies with periodic density functional theory calculations is used to provide a complete assignment of the vibrational spectra of this unusual species. The similarity between the Raman spectra of the compound and that of elemental sulfur is particularly striking. Copyright © 2009 John Wiley & Sons, Ltd.     

Elastic and Raman scattering of 8.5–11.4 MeV photons from 159Tb, 165Ho and 237Np

Differential cross sections for elastic and inelastic Raman scattering from the deformed heavy nuclei ¹⁵⁹Tb, ¹⁶⁵Ho and ²³⁷Np were measured at five energies between 8.5 and 11.4 MeV. Angular distributions at four angles between 90° and 140° for both elastic and inelastic scattering at 9.0 and 11.4 MeV were also measured. The monoenergetic photons were obtained from thermal neutron capture in Ni and Cr. All the angular distributions and the elastic and Raman scattering at the higher energies are in good overall agreement with theoretical predictions. The theory is based on a modified simple rotator model of the giant dipole resonance in which the effect of Delbrück scattering was included. A trend of both the elastic and Raman scattering at lower energies to be stronger than expected are suggested by the data. However, the ratio between the Raman and elastic scattering seem to be in good agreement with theory throughout the whole energy range. This shows that there is no need to introduce a direct nonresonant component to the imaginary part of the elastic scattering amplitude to explain the experimental data.     

Improvement in the calculation of anti-Stokes energy transfer and experimental justification based on Er0.01YbxY1 - 0.01 - xVO4 crystal

The improvement on the calculation of anti-Stokes energy transfer rate is studied in the present work. The additional proportion coefficient between Stokes and anti-Stokes light intensities of quantum Raman scattering theory as compared with the classical Raman theory is introduced to successfully describe the anti-Stokes energy transfer. The theoretical formula for the improvement on the calculation of anti-Stokes energy transfer rate is derived for the first time in this study. The correctness of introducing coefficient exp{△E/kT } from well-known Raman scatter theory is demonstrated also. Moreover, the experimental lifetime measurement in Er0.01YbxY1-0.01-xVO4 crystal is performed to justify the validity of our important improvement in the original phonon-assisted energy transfer theory for the first time.     

分子极性对类胡萝卜素共振拉曼光谱的影响

测量了非极性分子β胡萝卜素和极性分子角黄素, 在非极性溶剂CS₂和极性溶 剂1,2二氯乙烷中243–293 K的温度范围内的共振拉曼光谱. 结果表明, 溶质和溶剂的极性对拉曼光谱影响很大. 非极性分子β胡萝卜素在非极性溶剂CS₂中的拉曼散射截面最大, 线宽最窄, 而极性分子角黄素在极性溶剂1,2二氯乙烷中的拉曼散射截面最小, 线宽最大. 用溶剂效应及线性多烯分子的“相干弱阻尼电子-晶格振动”, “有效共轭长度”模型给予了解释.