Probe Raman spectroscopy in photon traps

It was found that the use of multifiber probes and photon traps allows contactless measurement of Raman scattering spectra for small amounts (～1 µg) of organic and inorganic compounds at exposures of 1–16 s. The possibility of improving the sensitivity of Raman scattering spectrum measurement using globular photonic crystals as matrices or substrates carrying analyzed compounds was studied.     

Raman scattering from microcrystals

This review discusses the size effects on Raman scattering from microcrystals. For ionic microcrystals, the existence of surface phonon modes is predicted from electromagnetic theories. It is shown that Raman spectroscopy is very effective to detect the surface phonon modes. The size effects on nonpolar phonons in covalent microcrystals can also be studied by Raman spectroscopy. However, the relaxation of the wave-vector selection rule or the phonon confinement explains only some of the experimental data. Development of lattice dynamical theories of Raman scattering from microcrystals including surface effects is highly required. Enhancement of Raman intensities arising from the excitation of electromagnetic normal modes of microcrystals is also discussed.     

Amorphous-like Raman spectra of semiconductor microcrystals

The size dependence of Raman scattering from gas-evaporated Si, Ge and GaP microcrystals, for which a free boundary condition can be assumed, has been investigated. As the microcrystals become sufficiently small (smaller than about 100A), spectra very similar to those of amorphous materials are observed, even though electron microscopy proves that they are crystalline. The amorphous-like Raman signals are believed to come from the surface layers of microcrystals.     

Amorphous-like Raman spectra of GaP microcrystals

Raman scattering from gas-evaporated GaP microcrystals smaller than about 400 Å has been investigated. As the crystalline size decreases from ～400 to ～170 Å, drastic changes in the Raman spectrum are observed; the TO and surface phonon peaks broaden and shift, and they strongly overlap with each other, finally transforming into a broad structure; broad bands located at around 80 and 200 cm^-1 appear and grow rapidly. The microcrystals smaller than about 250 Å show spectra very similar to those of amorphous GaP, even though the electron diffraction patterns prove that they are crystalline. The amorphous-like Raman signals seem to come from the surface layers of the microcrystals.     

Raman spectroscopy of smithsonite

Raman spectroscopy at both 298 and 77 K has been used to study a series of selected natural smithsonites from different origins. An intense sharp band at 1092 cm⁻¹ is assigned to the CO₃²⁻ symmetric stretching vibration. Impurities of hydrozincite are identified by a band around 1060 cm⁻¹. An additional band at 1088 cm⁻¹ which is observed in the 298 K spectra but not in the 77 K spectra is attributed to a CO₃²⁻ hot band. Raman spectra of smithsonite show a single band in the 1405–1409 cm⁻¹ range assigned to the ν₃ (CO₃)²⁻ antisymmetric stretching mode. The observation of additional bands for the ν₃^g modes for some smithsonites is significant in that it shows distortion of the ZnO₆ octahedron. No ν₂ bending modes are observed for smithsonite. A single band at 730 cm⁻¹ is assigned to the ν₄ in phase bending mode. Multiple bands be attributed to the structural distortion are observed for the carbonate ν₄ in phase bending modes in the Raman spectrum of hydrozincite with bands at 733, 707 and 636 cm⁻¹. An intense band at 304 cm⁻¹ is attributed to the ZnO symmetric stretching vibration. Copyright © 2007 John Wiley & Sons, Ltd.     

Raman spectroscopy of surfaces

Raman scattering has usually a very low efficiency. Therefore, during the first five decades after its discovery, Raman spectroscopic investigations of adsorbate-covered surfaces (except surfaces of highly porous samples) were out of reach. This changed in 1970s, when for molecules adsorbed on some surfaces, very large increase of the intensity of Raman spectrum (denoted as surface-enhanced Raman spectroscopy – SERS) was reported. In the past decade, two other very important achievements in surface Raman spectroscopy have been made: observation of SER spectrum of a single molecule and coupling of Raman spectroscope with the scanning probe microscope (STM or AFM) allowing a significant increase in the spatial resolution of Raman measurements in so-called tip-enhanced Raman spectroscopy (TERS). In the latter approach, fine tip made of a metal that supports surface plasmon resonances (such tip may be treated as a very local electromagnetic resonator) is brought at the nanometer distance above the surface, which induces large increase of the Raman scattering from molecules adsorbed at a surface located underneath the tip. This short review presents an overview of the state of the art and further possible applications of Raman spectroscopy in surface analysis. We mainly focus on SERS and TERS. Future prospects in these fields are also discussed.     

Matrix isolation Raman spectroscopy

A new primary laboratory measurement is described for testing field standards and measurement techniques used to detect trace amounts of toxic organic substances in water.     

Ultrafast Raman loss spectroscopy

This paper deals with a new form of nonlinear Raman spectroscopy called ‘ultrafast Raman loss spectroscopy (URLS)’. URLS is analogous to stimulated Raman spectroscopy (SRS) but is much more sensitive than SRS. The signals are background (noise) free unlike in coherent anti‐Stokes Raman spectroscopy (CARS) and it provides natural fluorescence rejection, which is a major problem in Raman spectroscopy. In addition, being a self‐phase matching process, the URLS experiment is much easier than CARS, which requires specific phase matching of the laser pulses. URLS is expected to be alternative if not competitive to CARS microscopy, which has become a popular technique in applications to materials, biology and medicine. Copyright © 2009 John Wiley & Sons, Ltd.     

Femtosecond stimulated Raman spectroscopy

Advances in the field of Femtosecond Stimulated Raman Spectroscopy (FSRS), a new time‐resolved structural technique that provides complete vibrational spectra on the ultrafast timescale, are reviewed. When coupled with a femtosecond optical trigger, the time evolution of a reacting species can be monitored with unprecedented <25 femtosecond temporal and 5 cm^‐1 spectral resolution. New technological and theoretical advances including the development of tunable FSRS and a background‐free FSRS format are discussed. The most recent experimental studies focus on ultrafast reaction dynamics in electronically excited states: isomerization in cyanobacterial phytochrome, ultrafast spin flipping in a solar cell sensitizer, and excited state proton transfer in green fluorescent protein. The use of FSRS to directly map multidimensional reactive potential energy surfaces and to probe the mechanism of reactive internal conversion is prospectively discussed.     

Subwavelength-resolution near-field Raman spectroscopy

The resolution capabilities of near-field Raman spectroscopy based on a giant enhancement of the electric field near a nanosized metal probe are studied. As a test sample, bundles of single-walled carbon nanotubes deposited on glass substrates are used. It is shown that this method ensures a subwavelength spatial resolution of about 50 nm and demonstrates a Raman scattering enhancement of the order of 10⁴.     

Wide area Raman spectroscopy

Raman spectroscopy allows nondestructive analysis of materials using laser illumination. However, most Raman spectrometers can only provide good signal levels and sufficient spectral resolution, by focusing the laser to micrometer-sized spots. This equates to enormous laser intensities, which for samples with even very minor optical absorption either means destroying or damaging it by absorbing even a tiny fraction of the laser power, or it means reducing the laser intensity and hence the signal level. Furthermore, Raman signals generated above or below the focal plane are rejected in traditional Raman spectrometers. As signal levels are already extremely low in Raman spectroscopy, several schemes offer an alternative to focusing down to a diffraction-limited spot, to increase the area by up to 6 orders of magnitude, and increase the sampling depth. This review describes and compares these schemes, and estimates the typical illumination areas.     

Laser spectroscopy : 5. Raman spectroscopy

This article in the series reviews the application of lasers in Raman spectroscopy.     

Characterization of sodium alginate and its block fractions by surface‐enhanced Raman spectroscopy

The surface‐enhanced Raman scattering (SERS) of sodium alginates and their hetero‐ and homopolymeric fractions obtained from four seaweeds of the Chilean coast was studied. Alginic acid is a copolymer of β‐D ‐mannuronic acid (M) and α‐L guluronic acid (G), linked 1 → 4, forming two homopolymeric fractions (MM and GG) and a heteropolymeric fraction (MG). The SERS spectra were registered on silver colloid with the 632.8 nm line of a He Ne laser. The SERS spectra of sodium alginate and the polyguluronate fraction present various carboxylate bands which are probably due to the coexistence of different molecular conformations. SERS allows to differentiate the hetero‐ and homopolymeric fractions of alginic acid by characteristic bands. In the fingerprint region, all the poly‐D ‐mannuronate samples present a band around 946 cm⁻¹ assigned to C O stretching, and C C H and C O H deformation vibrations, a band at 863 cm⁻¹ assigned to deformation vibration of β‐C₁ H group, and one at 799–788 cm⁻¹ due to the contributions of various vibration modes. Poly‐L ‐guluronate spectra show three characteristic bands, at 928–913 cm⁻¹ assigned to symmetric stretching vibration of C O C group, at 890–889 cm⁻¹ due to C C H, skeletal C C, and C O vibrations, and at 797 cm⁻¹ assigned to α C₁ H deformation vibration. The heteropolymeric fractions present two characteristic bands in the region with the more important one being an intense band at 730 cm⁻¹ due to ring breathing vibration mode. Copyright © 2009 John Wiley & Sons, Ltd.     

Diffusive motion of iron microcrystals studied by Mössbauer spectroscopy

A new model is presented which explains well the dramatic decrease of the Mössbauer line intensities with raising temperatures for freely dispersed iron microscrystals. In contrast to other theories which consider mainly vibration to be responsible we discuss here the decrease in terms of large amplitude diffusive rotational or translational jumps of the particles. Such diffusive jumps lead — in agreement with the observation — to a strong reduction of the Mössbauer-intensity without broadening the line width in a noticeable way. The typical potential well for a diffusing particle in an equilibrium position is derived quantitatively to be 13 meV. The model might be important also for a new understanding of the dynamics of catalytic clusters either in contact with each other or with larger solid surfaces.Part of this work was supported by the DFG Sonderforschungsbereich 306, Konstanz     

Raman spectroscopy of ZnS nanostructures

We report Raman scattering results of wurtzite ZnS nanowires, nanocombs, and nanobelts. The Raman spectrum obtained from ZnS nanowires exhibits first‐order phonon modes at 272, 284, and 350 cm⁻¹, corresponding to A₁/E₁ transverse optical, E₂ transverse optical, and A₁/E₁ longitudinal optical phonons, respectively. Several multiphonon modes are also observed. The longitudinal optical phonon mode varies in wavenumber for nanocombs and nanobelts, indicating that the residual strain varies during the morphological change from ZnS nanowires to nanocombs and ultimately to nanobelts. Interestingly, a surface optical (SO) phonon mode varies in wavenumber depending on the shape and surface roughness of the ZnS nanostructures. The surface modulation wavelengths of the ZnS nanowires, nanocombs, and nanobelts are estimated using the SO phonon dispersion relations and the observed SO phonon wavenumbers. Copyright © 2012 John Wiley & Sons, Ltd.     

Raman spectroscopy of atomic fluorine

We have measured the Raman scattering cross section of atomic fluorine for transitions between the ground fine-structure electronic states. The fluorine was contained a in heated, static chamber. Gas temperature, determined from the rotational Raman spectrum of molecular fluorine, was used as an input to calculate the degree of fluorine dissociation (assuming thermodynamic and chemical equilibrium). The Raman frequency shift and depolarization ratio were also determined. Our results indicate that Raman scattering can be used as a probe for atomic fluorine.     

Raman spectroscopy of carbon nanotubes

The use of Raman spectroscopy to reveal the remarkable structure and the unusual electronic and phonon properties of single wall carbon nanotubes (SWNTs) is reviewed comprehensively. The various types of Raman scattering processes relevant to carbon nanotubes are reviewed, and the theoretical foundations for these topics are presented. The most common experimental techniques used to probe carbon nanotubes are summarized, followed by a review of the novel experimental findings for each of the features in the first order and second order Raman spectra for single wall carbon nanotubes. These results are presented and discussed in connection with theoretical considerations. Raman spectra for bundles of SWNTs, for SWNTs surrounded by various common wrapping agents, and for isolated SWNTs at the single nanotube level are reviewed. Some of the current research challenges facing the field are briefly summarized.     

酿造酒的激光拉曼光谱

用激光拉曼光谱的方法对市场销售的几种酿造酒进行了研究，对酿造酒的拉曼光谱的归属进行了设定，并指出了拉曼光谱对鉴别酒的质量所具有的意义