Lasers in Raman spectroscopy

It is certainly no exaggeration to say that the application of lasers in Raman spectroscopy has revolutionized this field, giving new impetus to many investigations and opening up new areas of research. There are several reasons why lasers are in many cases superior to conventional lamps. 

If the incident radiation is plane-polarized, such as that produced by lasers in Raman spectroscopy, scattering theory predicts that totally symmetric modes... 

The absolute differential scattering cross section of the standard needs to be determined as precisely as possible. A number of measurements has been performed ovm-the past forty years [260,278-287]. The introduction of lasers in Raman spectroscopy and of computer processing of spectral data has improved highly the accuracy of Raman intensity measurements. As a result, the absolute differential Raman scattering cross section of nitrogen reported frrom different laboratories deviates within a few percent only [260,284,285,287]. 

Due to the very high intensity of the laser beams and their coherent nature they may be used in a variety of ways where controlled energy is required. Lasers are used commercially for excitation with a specific energy, e.g. in Raman spectroscopy or isotope separation. 

The 70 years since these first observations have witnessed dramatic developments in Raman spectroscopy, particularly with the advent of lasers. By now, a large variety of Raman spectroscopies have appeared, each with its own acronym. They all share the conunon trait of using high energy ( optical ) light to probe small energy level spacings in matter. 

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. 

Lasers having wavelengths ranging from the deep uv to the near infrared have been used in Raman spectroscopy. In industrial laboratories, the most common laser is the Nd YAG operating at 1.06 pm. Increasingly, diode lasers or other lasers operating in the 750—785-nm region are encountered. These... 

Raman spectroscopy, long used for quaHtative analysis, has been revitalized by the availabiHty of laser sources. Raman spectroscopy is based on scattering of light with an accompanying shift in frequency. The amount by which the frequency is shifted is characteristic of the molecules that cause the scattering. Hence, measurement of the frequency shift can lead to identification of the material. 

Laser stimulation of a silver surface results in a reflected signal over a million times stronger than that of other metals. Called laser-enhanced Raman spectroscopy, this procedure is useful in catalysis. The large neutron cross section of silver (see Fig. 2), makes this element useful as a thermal neutron flux monitor for reactor surveillance programs (see Nuclearreactors). 

UV-Vis spectroscopy may also provide valuable information if small molecules are studied. However, the photochemical sensitivity of many sulfur-containing molecules may trigger changes in the composition of the sample during irradiation. For instance, this phenomenon has been observed in Raman spectroscopy using the blue or green hnes of an argon ion laser which sometimes decompose sensitive sulfur samples with formation of Sg [2, 3]. Reliable spectra are obtained with the red hnes of a krypton ion or a He-Ne laser as well as with the infrared photons of a Nd YAG laser. 

The large energy differences between the global minimum structure of C2v symmetry and the other isomers indicate that equilibrium sulfur vapor will contain only minute amounts of the latter, even at very high temperatures. However, under non-equilibrium conditions as in electrical discharges or by illumination with a laser as in Raman spectroscopy unstable isomers may be formed and detected. 

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. 

An interesting and powerful new development in Raman spectroscopy of catalysts is the use of a UV laser to excite the sample. This has two major advantages. First, the scattering cross section, which varies with the fourth power of the frequency, is substantially increased. Second, the Raman peaks shift out of the visible region of the spectrum where fluorescence occurs. The reader is referred to Li and Stair for applications of UV Raman spectroscopy on catalysts [40]. 

Figure 9.27 In Raman spectroscopy, light from a laser is shone at a sample. It is monochromated at a frequency of v0. Most of the light is transmitted. Most of the scattered light is scattered elastically, so its frequency remains at v0 this is Rayleigh scattered light. Raman scattered light has a frequency V(SCattered) = v0 — vibration) The sample is generally in solution...

Applications of the Laser , CRC Press, Cleveland, Ohio (1973), 121—26 (Lasers in the Military) 17) Z. Iqbal, Advances in Raman Spectroscopy , Heyden, London, Chapt 23 (1973) 18) Z. Iqbal, JChemPhys 59, 1769... 

Lasers come next, not because of their intrinsic construction and mode of operation, but because they open up new dimensions of technique, precision, and scale. The experimental technique of physical chemistry that has benefited most from the laser is Raman spectroscopy, which barely existed before their introduction and is now in full flower, showing enormously detailed and interesting information about bulk matter and surfaces. A technique that was essentially invented by the laser is femtochemistry, where we can catch atoms red-handed in the act of reaction. Lasers have brought us right to the heart of reactions, and as such we must build them into our courses. 

He/Ne laser focussed into a small tapered hole in a pellet of the plastic. The flux density achieved at the focus was about 1000 Watts/cma. The scattered radiation was examined using a double spectrometer and photon-counting detection. A very fine spectrum, superior even to that of Maklakov and Nikitin (see Table 1), was recorded photo-electrically. Schaufele pointed out that a band atAv= 109cm-1 forecast previously by Tadokoro et aL (15) was not observed at first but in a note added in proof he mentions that a feature may be genuine at 98 2 cm-1. A band had already been observed at Av= 110cm-1 by instrument developers at the Cary Instrument Co. since Szymanski (16) shows a spectrum of isotactic polypropylene, recorded at Monrovia, Calif., on a laser sourced Cary 81 spectrometer, as an example of recent advances in Raman spectroscopy. 

Since its development by Delhaye and Dhamelincourt in 1975 [1] the epi-illumination Raman microprobe has become one of the most important input systems in Raman spectroscopy and is the instrument around which most Raman imaging systems are constructed. Epi-illumination instruments are almost always constructed around research-grade commercially available fluorescence microscope frames, with input optics modified to accept an exciting laser and with output optics modified to direct backscattered Raman signal to a spectrograph. 

The Fourier transform Raman spectrometer is constructed around an interferometer (see Figure 4.20) [57], Normally, a continuous wave Nd YAG laser (1064nm) is used for the sample excitation. In relation to the sample arrangement inside the spectrometer, there are two fundamental geometries in which a sample is tested in Raman spectroscopy, that is, the 90° geometry, where the laser beam... 

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