Vibrational Raman-scattering data

The inelastic processes - spontaneous Raman scattering (usually simply called Raman scattering), nonlinear Raman processes, and fluorescence - permit determination of species densities as well as temperature, and also allow one, in principle, to determine the temperature for particular species whether or not in thermal equilibrium. In Table II, we categorize these inelastic processes by the type of the information that they yield, and indicate the types of combustion sources that can be probed as well as an estimate of the status of the method. The work that we concentrate upon here is that indicated in these first two categories, viz., temperature and major species densities determined from vibrational Raman scattering data. The other methods - fluorescence and nonlinear processes such as coherent anti-Stokes Raman spectroscopy - are discussed in detail elsewhere (5). 

Temperature-Velocity Correlation Measurements for Turbulent Diffusion Flames from Vibrational Raman-Scattering Data... 

These are the quantities to which we are giving our attention. Vibrational Raman scattering is being used for the temperature and density data, and, when taken simultaneously with velocity data from coupled LV instrumentation (.8), provides also the fluctuation mass flux through use of fast chemistry assumptions and the ideal gas law for atmospheric pressure flames. 

Figure 3. Schematic of turbulent combustor geometry and optical data acquisition system for vibrational Raman-scattering temperature measurements using SAS intensity ratios. Also shown are sketches of the expected Raman contours viewed by each of the photomultiplier detectors, the temperature calibration curve, and several expected pdf s of temperature at different flame radial positions. The actual SAS temperature calibration curve was calculated theoretically to within a constant factor. This constant, which accounted for the optical and electronic system sensitivities, was determined experimentally by means of SAS measurements made on a premixed laminar flame of known temperature. Measurements of Ne concentration were made also with this apparatus, based on the integrated Stokes vibrational Q-branch intensities. These signals were related to gas densities by calibration against ambient air signals.

We present here preliminary results for the (temperature x vj ljjcity) probability density function shown in this paper as , where the quantities within the average brackets are instantaneous values. These data have been obtained from a coordinated experimental program utilizing pulsed laser vibrational Raman scattering and cw real fringe laser velocimetry (LV). 

Laser Raman Microprobe. A more sophisticated microscope is the Laser Raman Microprobe, sometimes referred to as MOLE (the molecular orbital laser examiner). This instmment is designed around a light microscope to yield a Raman spectmm (45) on selected areas or particles, often <1 ia volume. The data are related, at least distantly, to iafrared absorption, siace the difference between the frequency of the exciting laser and the observed Raman frequency is the frequency of one of the IR absorption peaks. Both, however, result from rotational and vibrational states. Unfortunately, strong IR absorption bands are weak Raman scatterers and vice versa hence there is no exact correspondence between the two. 

Hydrogen is the most abundant chemical element in the universe, and in its various atomic and molecular forms furnishes a sensitive test of all of experimental, theoretical and computational methods. Vibration-rotational spectra of dihydrogen in six isotopic variants constituting all binary combinations of H, D and T have nevertheless been recorded in Raman scattering, in either spontaneous or coherent processes, and spectra of HD have been recorded in absorption. Despite the widely variable precision of these measurements, the quality of some data for small values of vibrational quantum number is still superior to that of data from electronic spectra [106], almost necessarily measured in the ultraviolet region with its concomitant large widths of spectral lines. After collecting 420... 

Based partly on UV-vis absorption but mostly on surface-enhanced Raman scattering (SERS) data, the electrochemical oxidation product from 9-hydroxyellipticine (9-OH-E) 13a at Pt and Ag electrodes and that from A -methyl-9-hydroxyellipticinium cation (NMHE) 13b at those electrodes and also by horseradish peroxidase-H2O2 were studied and their structures identified <1996JRS539>. The products, 9-oxoellipticine (9-oxo-E) 14a from 9-OH-E and A -methyl-9-oxoellipticinium cation (NMOE) 14b from NMHE both have quinone-imine structures readily identified from the vibrational analysis of their SERS spectra. 

In contrast, recent work (4-12) has shown that Raman spectroscopy can be used to study Ti) adsorption on oxides, oxide supported metals and on bulk metals [including an unusual effect sometimes termed "enhanced Raman scattering" wherein signals of the order of 10 - 106 more intense than anticipated have been reported for certain molecules adsorbed on silver], (ii) catalytic processes on zeolites, and (iii) the surface properties of supported molybdenum oxide desulfurization catalysts. Further, the technique is unique in its ability to obtain vibrational data for adsorbed species at the water-solid interface. It is to these topics that we will turn our attention. We will mainly confine our discussion to work since 1977 (including unpublished work from our laboratory) because two early reviews (13,14) have covered work before 1974 and two short recent reviews have discussed work up to 1977 (15,16). 

Coherent anti-Stokes Raman scattering (CARS) microscopy is an emerging technology. By tuning a pump laser and a Stokes laser to a Raman-active molecular vibration, molecular selectivity and faster measurement speed can be obtained. This approach has been used to track the phase segregation, crystallisation and dissolution of paclitaxel from biocompatible excipients and films providing kinetic data not achievable through standard Raman microscopy methods [56]. 

All data were processed by a central computer to derive both temperature and species concentrations. The details of these computer fits are identical to those described elsewhere (10, 11) with the exception that a vibrational partition function correction was included in the analysis of the data. The absolute mole fractions of fuel, 0 CO, H2, C0 , and H2O were determined by flowing known concentrations of these gases mixed with known concentrations of N2 through the burner. A comparison of the intensity of the N2 Raman spectrum intensity to the Raman spectrum intensity of any of the other gases provided an absolute calibration for all laser Raman scattering flame studies. 

Table 3.32 Calculated data relevant to polarizabilities in water dimer for intramolecular vibrational modes, and Raman scattering activities. ... 

The experimental data was fitted, as shown in Fig. 5.10, to a convolution of this response function with the instrument response function. As the result, the decay time T-2/2 was estimated to be 1.1 0.1 ps. Recently, the population lifetime Ti of G-phonons was measured by incoherent time-resolved anti-Stokes Raman scattering and the lifetime was found to be 1.1-1.2 ps in semiconducting SWNTs [57]. Therefore, one can reasonably assume ipu Ti at room temperature. This result is consistent with the conventional Raman line width of semiconducting SWNTs [58]. The observed short lifetime of the G-phonons implies anharmonic mode coupling between G-phonons and RBM-phonons [59]. In fact, a frequency modulation of the G mode by the RBM has been reported, suggesting the anharmonic coupling between these vibrations [56]. 

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