Resonant Raman effect

The excitation in the deep-UV results in more intense Raman scattering. Deep-UV laser excitation has the ability to avoid fluorescence background in the Raman spectra. Tunability of the UV source could allow exploitation of resonance Raman effect. Resonance Raman Effect enhances the intensity of Raman lines. Deep-UV LIF is... 

This spectrum is called a Raman spectrum and corresponds to the vibrational or rotational changes in the molecule. The selection rules for Raman activity are different from those for i.r. activity and the two types of spectroscopy are complementary in the study of molecular structure. Modern Raman spectrometers use lasers for excitation. In the resonance Raman effect excitation at a frequency corresponding to electronic absorption causes great enhancement of the Raman spectrum. 

In the following sections, we first show the phonon dispersion relation of CNTs, and then the calculated results for the Raman intensity of a CNT are shown as a function of the polarisation direction. We also show the Raman calculation for a finite length of CNT, which is relevant to the intermediate frequency region. The enhancement of the Raman intensity is observed as a function of laser frequency when the laser excitation frequency is close to a frequency of high optical absorption, and this effect is called the resonant Raman effect. The observed Raman spectra of SWCNTs show resonant-Raman effects [5, 8], which will be given in the last section. 

The resonance Raman effect — review of the theory and of applications in inorganic chemistry. R. J. H. Clark and B. Stewart, Struct. Bonding (Berlin), 1979, 36, 1-80 (110). 

Clarke RJH, Stewart B (1979) The Resonance Raman Effect. Review of the Theory and of AppUcations in Inorganic Chemistty 36 1-80... 

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.

Raman spectroscopy is primarily useful as a diagnostic, inasmuch as the vibrational Raman spectrum is directly related to molecular structure and bonding. The major development since 1965 in spontaneous, c.w. Raman spectroscopy has been the observation and exploitation by chemists of the resonance Raman effect. This advance, pioneered in chemical applications by Long and Loehr (15a) and by Spiro and Strekas (15b), overcomes the inherently feeble nature of normal (nonresonant) Raman scattering and allows observation of Raman spectra of dilute chemical systems. Because the observation of the resonance effect requires selection of a laser wavelength at or near an electronic transition of the sample, developments in resonance Raman spectroscopy have closely paralleled the increasing availability of widely tunable and line-selectable lasers. 

The first laser Raman spectra were inherently time-resolved (although no dynamical processes were actually studied) by virtue of the pulsed excitation source (ruby laser) and the simultaneous detection of all Raman frequencies by photographic spectroscopy. The advent of the scanning double monochromator, while a great advance for c.w. spectroscopy, spelled the temporary end of time resolution in Raman spectroscopy. The time-resolved techniques began to be revitalized in 1968 when Bridoux and Delhaye (16) adapted television detectors (analogous to, but faster, more convenient, and more sensitive than, photographic film) to Raman spectroscopy. The advent of the resonance Raman effect provided the sensitivity required to detect the Raman spectra of intrinsically dilute, short-lived chemical species. The development of time-resolved resonance Raman (TR ) techniques (17) in our laboratories and by others (18) has led to the routine TR observation of nanosecond-lived transients (19) and isolated observations of picosecond-timescale events by TR (20-22). A specific example of a TR study will be discussed in a later section. 

In the case of polyenes, the term I scattering is dominant in the Raman spectra resonant with the 1 flu excited states22,26 the contribution of the term m scattering is important in the Raman spectra resonant with the 2 Ag excited states27. In addition, an interference effect between the 1 flu and 2 kg states in a Raman-intensity vs excitation-photon-energy plot (which is called an excitation profile) of the in-phase C=C stretch has been suggested28. 

Beattie, I.R., Ozin, G.A., and Perry, R.O., Gas phase Raman spectra of P4, P2, As4 and As2. Resonance fluorescence spectrum of 80Se2. Resonance fluores-cence-Raman effects in the gas-phase spectra of sulfur and iodine. Effect of pressure on the depolarization ratios for iodine,. Chem. Soc., Perkin I, 2071, 1970. 

Experimentally, several precautions must be taken if reliable Raman data are to be obtained from solution studies. Firstly, the instrumental slit-width should be appreciably smaller than the half-width of the band to be studied. This means that slits wider than 2 cm-1 are to be avoided. Secondly, photolytic decomposition of the sample and local boiling of the solvent have also to be avoided. Careful choice of laser frequencies, use of a low incident power and, if necessary, sample spinning are indicated. The need for a relatively high solute concentration usually means that there is little choice of solvent. Particularly for coloured samples the presence of a vestigal resonance Raman effect must be tested by measurements with a variety of... 

In addition to experiments which were possible with conventional lamps but can be much more easily performed with lasers, there are some investigations which have to be done within certain exposure times or signal-to-noise ratios and these have only been possible since lasers have been developed. This group includes the electronic Raman effect 195-197) observation of Raman scattering in metals where the scattering quasi particles are phonons, Raman studies of vibrational spectra in semiconductor crystals or the resonance Raman effect 200-202)... 

When the frequency of a laser falls fully into an absorption band, multiple phonon processes start to appear. Leite et al 2° ) observed /7 h order ( = 1, 2. 9) Raman scattering in CdS under conditions of resonance between the laser frequency and the band gap or the associated exciton states. The scattered light spectrum shows a mixture of fluorescent emission and Raman scattering. Klein and Porto 207) associated the multiphonon resonance Raman effect with the fluorescent emission spectrum, and suggested a possible theoretical approach to this effect. 

Resonance Raman effects in halogen gases have been observed by Holzer etal. 207a). with an appropriate choice of exciting lines from an argon laser either resonance Raman effect or resonance fluorescence could be observed. The difference between the two spectra is discussed. In the case of a strong resonance Raman effect, overtone sequences up to the 14 harmonic could be observed. 

Figure 1. Diagrams of potential energy, V, versus Internuclear separation, q, for a molecule undergoing vibrational excitation by (a) the Raman effect or (b) a resonance Raman effect (hVfj-hvg) or a pre-resonance effect h >

The exact features of molecular and electronic structure which give rise to the resonance Raman effect are not well understood. 

The Resonance Raman Effect (RRE) ca be observed when a molecule is excited by light with a frequency which falls under an obsorption band of the molecule. Whereas an excitation of this type commonly produces fluorescence for the gas phase, the fluorescence is usually suppressed for solutions, pure liquids, and sohd state samples. The Pre-Resonance Raman Effect (PRRE) is observed if the exciting line comes close to, but is not overlapping with an absorption band. 

For our purpose, it is convenient to classify the measurements according to the format of the data produced. Sensors provide scalar valued quantities of the bulk fluid i. e. density p(t), refractive index n(t), viscosity dielectric constant e(t) and speed of sound Vj(t). Spectrometers provide vector valued quantities of the bulk fluid. Good examples include absorption spectra A t) associated with (1) far-, mid- and near-infrared FIR, MIR, NIR, (2) ultraviolet and visible UV-VIS, (3) nuclear magnetic resonance NMR, (4) electron paramagnetic resonance EPR, (5) vibrational circular dichroism VCD and (6) electronic circular dichroism ECD. Vector valued quantities are also obtained from fluorescence I t) and the Raman effect /(t). Some spectrometers produce matrix valued quantities M(t) of the bulk fluid. Here 2D-NMR spectra, 2D-EPR and 2D-flourescence spectra are noteworthy. A schematic representation of a very general experimental configuration is shown in Figure 4.1 where r is the recycle time for the system. 

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