Spontaneous Raman

The only modification of equation (Al.6.90) for spontaneous Raman scattering is the multiplication by the density of states of the cavity, equation (Al.6.24). leading to a prefactor of the fonn cojCOg. ... 

Conventional spontaneous Raman scattering is the oldest and most widely used of the Raman based spectroscopic methods. It has served as a standard teclmique for the study of molecular vibrational and rotational levels in gases, and for both intra- and inter-molecular excitations in liquids and solids. (For example, a high resolution study of the vibrons and phonons at low temperatures in crystalline benzene has just appeared [38].)... 

The unique feature in spontaneous Raman spectroscopy (SR) is that field 2 is not an incident field but (at room temperature and at optical frequencies) it is resonantly drawn into action from the zero-point field of the ubiquitous blackbody (bb) radiation. Its active frequency is spontaneously selected (from the infinite colours available in the blackbody) by the resonance with the Raman transition at co - 0I2 r material. The effective bb field mtensity may be obtained from its energy density per unit circular frequency, the... 

This basic instrumentation, here described within the context of spontaneous Raman scahering, may be generalized to most of the other Raman processes that are discussed. Specific details can be found in the citations. 

Nonnal spontaneous Raman scahering suffers from lack of frequency precision and thus good spectral subtractions are not possible. Another limitation to this technique is that high resolution experiments are often difficult to perfomi [39]. These shortcomings have been circumvented by the development of Fourier transfomi (FT) Raman spectroscopy [40]. FT Raman spectroscopy employs a long wavelength laser to achieve viable interferometry. 

Coherent and spontaneous Raman spectroscopy in shocked and unshocked liquids NATO ASI Series C 184 425... 

The scattered radiation V3 is to high wavenumber of Vj (i.e. on the anti-Stokes side) and is coherent, unlike spontaneous Raman scattering hence the name CARS. As a consequence of the coherence of the scattering and the very high conversion efficiency to V3, the CARS radiation forms a collimated, laser-like beam. 

The selection mles for CARS are precisely the same as for spontaneous Raman scattering but CARS has the advantage of vastly increased intensity. 

Special Raman Spectroscopies. The weakness of Raman scattering results typically in the conversion of no more than 10 of the incident laser photons into a usable signal, limiting the sensitivity of conventional spontaneous Raman spectroscopy. This situation can be improved using alternative approaches (8,215,216). 

A spontaneous Raman spectra is shown in Figure 2.8d in which the on- and off-resonant frequencies are indicated. The DNA bundles are observed at the resonant frequency, as shown in Figure 2.8a, while they cannot be seen at the off-resonant frequency in Figure 2.8b. This indicates that the observed contrast is dominated by the vibrationally resonant CARS signals. Figure 2.8c shows a cross-section of Figure 2.8a denoted by two solid arrows, which were acquired with a 5 nm step. The FWHM of... 

The wavenumbers of the observed bands are identical with those of the spontaneous Raman spectrum of the solution and oxazine solid [27]. The impulsive stimulated Raman transition may initiate coherent vibrations in the electronic excited state. However, there was no sign of the excited-state vibrations superimposed on the ground-state bands in the spectrum of Figure 6.3. 

Laser-based methods of identification are extremely powerful they are able to provide species and structural information, as well as accurate system temperature values. Spontaneous Raman scattering experiments are useful for detection of the major species present in the system. Raman scattering is the result of an inelastic collision process between the photons and the molecule, allowing light to excite the molecule into a virtual state. The scattered light is either weaker (Stokes shifted) or... 

We will first discuss spontaneous Raman spectroscopy with lasers (linear Raman effect) and then briefly some investigations of the nonlinear Raman effect. 

There are several articles reviewing spontaneous Raman spectroscopy with lasers 191-194) extensive references to the literature up to 1968. This survey therefore will be restricted to a selection of recent work in this field in order to demonstrate the progress achieved. 

The linewidth depends on that of the exciting laser line and is often much narrower than the width of spontaneous Raman lines. 

Besides the spectroscopic investigations of solids by laser-excited spontaneous Raman or Brillouin scattering already discussed in Sections III.6 and 7, much new insight into the optical properties and the structure of solids has been gained by studying nonlinear optical effects. (Surveys and more detailed information about nonlinear optics can be found in refs. 306-308))... 

The spectral line shape in CARS spectroscopy is described by Equation (6.14). In order to investigate an unknown sample, one needs to extract the imaginary part of to be able to compare it with the known spontaneous Raman spectrum. To do so, one has to determine the phase of the resonant contribution with respect to the nonreso-nant one. This is a well-known problem of phase retrieval, which has been discussed in detail elsewhere (Lucarini et al. 2005). The basic idea is to use the whole CARS spectrum and the fact that the nonresonant background is approximately constant. The latter assumption is justihed if there are no two-photon resonances in the molecular system (Akhmanov and Koroteev 1981). There are several approaches to retrieve the unknown phase (Lucarini et al. 2005), but the majority of those techniques are based on an iterative procedure, which often converges only for simple spectra and negligible noise. When dealing with real experimental data, such iterative procedures often fail to reproduce the spectroscopic data obtained by some other means. 

FIGURE 6.19 Vibrational spectra of vanillin in isopropanol solntion. Bottom panel experimentally measnred CARS spectrum (1064 nm and continuum excitation, 1064 nm probe). Middle panel retrieved Raman spectrum. Top panel experimentally measured spontaneous Raman spectrum (excitation wavelength 532 nm). The acquisition time for CARS spectrum was 100 times shorter than for spontaneous Raman. The incident powers were set at approximately the same level. 

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