Raman laser spectroscopic methods

Apart from LIF, other laser-based HPLC detectors are LS and Raman. Laser spectroscopic methods for detection in LC have been reviewed [567]. 

Modern Raman laser spectroscopic methods can be used to study reactions that occur on the femtosecond (10 s) scale. On this very short time scale, even rapid molecule motions (e.g., bond vibrations and rotations about a bond) can be resolved. Such techniques are used to study activated complexes. 

In addition to laser fluorescence excitation, several other laser spectroscopic methods have been found to be useful for the state-selective and sensitive detection of products of reactive collisions resonance-enhanced multiphoton ionization [58], coherent anti-Stokes Raman scattering [M], bolometric detection with laser excitation [30], and direct infrared absorption [7]. Several additional laser techniques have been developed for use in spectroscopic studies or for diagnostics in reacting systems. Of these, four-wave mixing [ ] is applicable to studies of reaction dynamics although it does have a somewhat lower sensitivity than the techniques mentioned above. 

In this contribution we present two laser spectroscopic methods that use coherent resonance Raman scattering to detect rf-or laser -induced Hertzian coherence phenomena in the gas phase these novel coherent double resonance techniques for optical heterodyne detection of sublevel coherence clearly extend the above mentioned previous methods using incoherent light sources. In the case of Doppler broadened optical transitions new signal features appear as a result of velocity-selective optical excitation caused by the narrow-bandwidth laser. We especially analyze the potential and the limitations of the new detection schemes for the study of collision effects in double resonance spectroscopy. In particular, the effect of collisional velocity changes on the Hertzian resonances will be investigated. 

The same equipment, which is used for time-resolved Ivuninescence application is suitable for other laser-based spectroscopies. Thus several spectroscopic methods may be applied simultaneously. The most important techniques, which may be used together with time-resolved luminescence, are laser-induced breakdown spectroscopy, Raman spectroscopy and Second Harmonics Generation spectroscopy. 

Because chemical and structural properties of natural and artificial gems are very similar in this case, the possibilities of Raman and LIBS methods are rather limited. It was found that another laser-based techniques could be very effective for rapid spectroscopic discrimination between natural and synthetic emeralds, rubies, and alexandrite (Armstrong et al. 2000a,b). The first one is DRIFTS (Diffuse Reflectance Fourier Transformed Infra-Red Spectroscopy)... 

A major advance in the investigation of the intramolecular dynamics of spin equilibria was the development of the Raman laser temperature-jump technique (43). This uses the power of a laser to heat a solution within the time of the laser pulse width. If the relaxation time of the spin equilibrium is longer than this pulse width the dynamics of the equilibrium can be observed spectroscopically. At the time of its development only two lasers had sufficient power to cause an adequate temperature rise, the ruby laser at 694 nm and the neodymium laser at 1060 nm. Neither of these wavelengths is absorbed by solvents. Various methods were used in attempts to absorb the laser power, with partial success for microsecond relaxation times. 

Among a variety of spectroscopic methods, vibrational spectroscopy is most commonly used in structural chemistry. IR/Raman spectroscopy provides information about molecular symmetry of relatively small molecules and functional groups in large and complex molecules. Furthermore, Raman spectroscopy enables us to study the structures of electronically excited molecules and unstable species produced by laser photolysis at low temperatures. Several other applications that are important in structural chemistry are also discussed in this section. 

CLM method can also be combined with various kinds of spectroscopic methods. Fluorescence lifetime of an interfacially adsorbed zinc-tetra-phenylporphyrin complex was observed by a nanosecond time-resolved laser induced fluorescence method [25]. Microscopic resonance Raman spectrometry was also combined with the CLM. This combination was highly advantageous to measure the concentration profile at the interface and a bulk phase [14]. Furthermore, circular dichroic spectra of the liquid-liquid interface in the CLM could be measured [19]. 

Raman scattering was first observed in 1928 and was used to investigate the vibrational states of many molecules in the 1930s. Initially, spectroscopic methods based on the phenomenon were used in research on the structure of relatively simple molecules. Over the past 20 years, however, the development of laser sources and new generations of monochromators and detectors has made possible the application of Raman spectroscopy to the solution of many problems of technological interest. 

The current detailed understanding of photo-induced electron transfer processes has been advanced dramatically by the development of modern spectroscopic methods. For example, the application of time-resolved optical spectroscopy has developed from modest beginnings (flash-phyotolysis with millisecond resolution) [108,109] to the current state of the art, where laser spectroscopy with nanosecond resolution [110-113] must be considered routine, and where picosecond [114-116] or even femtosecond resolution [117] is no longer uncommon. Other spectroscopic techniques that have been applied to the study of electron transfer processes include time-resolved Raman spectroscopy [118], (time resolved) electron spin... 

Applications of IR and Raman spectroscopy to the study of clinkers and unhydrated cements have been reviewed (B39,B40). The laser Raman microprobe, with which regions of micrometre dimensions on a polished surface may be examined, has been used to investigate structure and crystallinity, especially of the alite and belite (Cl9). Spectroscopic methods for studying the surface structures and compositions of cements are considered in Section 5.6.2. 

The spectroscopic methods are based on time-resolved pump-probe schemes where the collision-free regime is usually attained by using low pressure conditions. Application of various linear and non-linear laser techniques, such as LIF (laser-induced fluorescence), REMPI (resonant-enhanced multiphoton ionization) and CARS (coherent antistokes Raman spectroscopy) have provided detailed information on the internal states of nascent reaction products [58]. Obviously, an essential prerequisite for the application of these techniques is the knowledge of the spectroscopic properties of the products. 

Thus far, we have examined vibrational spectroscopy using IR absorption spectroscopy, what we called in Ch. 3 one photon method , a general type that encompasses most experiments in spectroscopy. There exist, however, other types of spectroscopy to observe vibrations. These are for instance Raman spectroscopy, which is also of a current use in chemical physics and may be considered a routine method. Other less known methods are modem time-resolved IR spectroscopies. All these methods are two-photon or multiphoton spectroscopies. They do not involve a single photon, as in absorption, but the simultaneous absorption and emission of two photons, as in Raman and in other scattering experiments, or the successive absorption(s) and emission(s) of photons that are coherently delayed in time, as in time-resolved nonlinear spectroscopies. By coherently , we assume the optical waves that carry these two photons keep a well-defined phase difference. In this latter type of spectroscopy, we include all modem set-ups that involve time-controlled laser spectroscopic techniques. We briefly sketch the interest of these various methods for the study of H-bonds in the following subsections. 

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