Scattering Rayleigh, Raman

These contradictory results led Jonkman et al.21 to propose that non-resonant light scattering (NRLS) was responsible for the fast component. NRLS would yield decays that basically consisted of Raman-Rayleigh-scattered laser light together with the slower fluorescence decay. It would look like biexponential decay. Experiments where the laser was purposely detuned from the rotational line seemed to confirm their ideas.21... 

Figure Bl.2.2. Schematic representation of the polarizability of a diatomic molecule as a fimction of vibrational coordinate. Because the polarizability changes during vibration, Raman scatter will occur in addition to Rayleigh scattering.

The first temi results in Rayleigh scattering which is at the same frequency as the exciting radiation. The second temi describes Raman scattering. There will be scattered light at (Vq - and (Vq -i- v ), that is at sum and difference frequencies of the excitation field and the vibrational frequency. Since a. x is about a factor of 10 smaller than a, it is necessary to have a very efficient method for dispersing the scattered light. 

Due to the rather stringent requirements placed on the monochromator, a double or triple monocln-omator is typically employed. Because the vibrational frequencies are only several hundred to several thousand cm and the linewidths are only tens of cm it is necessary to use a monochromator with reasonably high resolution. In addition to linewidth issues, it is necessary to suppress the very intense Rayleigh scattering. If a high resolution spectrum is not needed, however, then it is possible to use narrow-band interference filters to block the excitation line, and a low resolution monocln-omator to collect the spectrum. In fact, this is the approach taken with Fourier transfonn Raman spectrometers. 

Perhaps the best known and most used optical spectroscopy which relies on the use of lasers is Raman spectroscopy. Because Raman spectroscopy is based on the inelastic scattering of photons, the signals are usually weak, and are often masked by fluorescence and/or Rayleigh scattering processes. The interest in usmg Raman for the vibrational characterization of surfaces arises from the fact that the teclmique can be used in situ under non-vacuum enviromnents, and also because it follows selection rules that complement those of IR spectroscopy. 

All three terms in this equation represent scattering of the radiation. The first term corresponds to Rayleigh scattering of unchanged wavenumber v, and the second and third terms correspond to anti-Stokes and Stokes Raman scattering, with wavenumbers of (v + 2v () and (v — 2v () respectively. 

Figure 5.16 Raman and Rayleigh scattering processes involving virtual states Fq and Fj...

The mechanism for Stokes and anti-Stokes vibrational Raman transitions is analogous to that for rotational transitions, illustrated in Figure 5.16. As shown in Figure 6.3, intense monochromatic radiation may take the molecule from the u = 0 state to a virtual state Vq. Then it may return to u = 0 in a Rayleigh scattering process or to u = 1 in a Stokes Raman transition. Alternatively, it may go from the v = state to the virtual state Fj and return to V = (Rayleigh) or to u = 0 (Raman anti-Stokes). Flowever, in many molecules at normal... 

In the low frequency region, the calculations predict nanotube-specifiic Eig and E g modes around 116 cm and 377 cm respectively, for (10,10) armchair naiiotubes, but their intensities are expected to be lower than that for the A g mode. However, these Eig and E2g modes are important, since they also show a diameter dependence of their mode frequencies. In the very low frequency region below 30 cm a strong low frequency Raman-active E2g mode is expected. However, it is difficult to observe Raman lines in the very low frequency region, where the background Rayleigh scattered is very strong. 

The moments are determined experimentally as for nitrogen in [5, 106] using Rayleigh and Raman depolarized scattering spectra. 

De Santis A., Sampoli M., Morales P, Signorelli G. Density evolution of Rayleigh and Raman depolarized scattering in fluid N2. Mol. Phys. 35, 1125-40 (1978). 

Figure 3.6. A simplified energy diagram illustrating the origins of Rayleigh scattering and of the Stokes and anti-Stokes lines in the Raman spectrum.

Figure 2.52 Schematic representation of the transitions giving rise to the Raman effect. GS = ground electronic state, ES = excited electronic state, VS = virtual electronic stale, R = Rayleigh scattering, S = transitions giving rise to Stokes lines, AS = transitions giving rise to Anti-Stokes lines, RRS = transitions giving rise to resonance Raman.

Similar to IR sensors, Raman sensors have profited from miniaturisation and improvement of light sources and optics. Essentially, a Raman sensor consists of (i) a monochromatic source, a (ii) sensor head, a (iii) filter separating the Raman lines from the excitation radiation and Rayleigh scattering and a (iv) spectral analyser. 

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