Laser-Raman spectroscopy instrumentation

Vibrational Spectroscopy. Infrared absorption spectra may be obtained using convention IR or FTIR instrumentation the catalyst may be present as a compressed disk, allowing transmission spectroscopy. If the surface area is high, there can be enough chemisorbed species for their spectra to be recorded. This approach is widely used to follow actual catalyzed reactions see, for example. Refs. 26 (metal oxide catalysts) and 27 (zeolitic catalysts). Diffuse reflectance infrared reflection spectroscopy (DRIFT S) may be used on films [e.g.. Ref. 28—Si02 films on Mo(llO)]. Laser Raman spectroscopy (e.g.. Refs. 29, 30) and infrared emission spectroscopy may give greater detail [31]. 

Dramatic improvements in instrumentation (lasers, detectors, optics, computers, and so on) have during recent years raised the Raman spectroscopy technique to a level where it can be used for species specific quantitative chemical analysis. Although not as sensitive as, for example IR absorption, the Raman technique has the advantage that it can directly measure samples inside ampoules and other kinds of closed vials because of the transparency of many window materials. Furthermore, with the use of polarization techniques, one can derive molecular information that cannot be obtained from IR spectra. Good starting references dealing with Raman spectroscopy instruments and lasers are perhaps [34-38]. 

Lasers. - The instrumentation comprising the state of the art in Raman spectroscopy has [vogressed at a remarkable rate in recent years. Modem day Raman spectroscopy has been commonly referred to as "laser" Raman spectroscopy to differentiate from the older method of inducing the Raman effect with mercury-arc lamps (emission lines at 435.8 and... 

The morphology, particle size and structure of the oxides were determined by using transmission electron microscopy (TEM) and X-ray powder diffraction (XRD). BET surface area of the samples were measured by using Micromeritics ASAP-2000 instrument. The interaction of Ce with Mo and its effect on the nature of active oxygen species in the complex oxides were studied by using temperature-programmed reduction(TPR) and laser Raman spectroscopy (LRS). 

Figure 10 Raman spectra of various mixtures of nitrogen and oxygen obtained with the spectrograph in Figure 9. For the sake of clarity the spectra have been vertically displaced from one another. The N2 peak is on the right. Band intensity is essentially from the pure vibrational mode. The rotational-vibrational side bands form weak overlapped wings on either side of the main peaks. Reproduced with permission of the Society of Photo-Optical Instrumentation Engineers (SPIE) from Gilbert AS, Hobbs KW, Reeves AH and Jobson PP (1994) Automated headspace analysis for quality assurance of pharmaceutical vials by laser Raman spectroscopy. Proceedings of the SPIE - Society of Photo-Optical Instrumentation Engineers 2248 391-398.

Early Raman spectroscopy instruments saw little forensic use. Illumination sources were mercury vapor lamps with filters that isolated specific mercury radiation wavelengths. Sample sizes were rather large and Raman spectra were captured on photographic film. The detection of weak spectral lines sometimes required days of operation and film exposure. Today s instruments use of laser... 

The first successful application of the continuous wave (CW) He-Ne gas laser as a Raman excitation source by Kogelnik and Porto (14) was reported in 1963. Since that time, significant improvements in instrumentation have been continually achieved which have circumvented a great number of problems encountered with mercury lamp sources. The renaissance of Raman spectroscopy has also been due to improvements in the design of monochromators and photoelectric recording systems. 

Since there are a large number of different experimental laser and detection systems that can be used for time-resolved resonance Raman experiments, we shall only focus our attention here on two common types of methods that are typically used to investigate chemical reactions. We shall first describe typical nanosecond TR spectroscopy instrumentation that can obtain spectra of intermediates from several nanoseconds to millisecond time scales by employing electronic control of the pnmp and probe laser systems to vary the time-delay between the pnmp and probe pnlses. We then describe typical ultrafast TR spectroscopy instrumentation that can be used to examine intermediates from the picosecond to several nanosecond time scales by controlling the optical path length difference between the pump and probe laser pulses. In some reaction systems, it is useful to utilize both types of laser systems to study the chemical reaction and intermediates of interest from the picosecond to the microsecond or millisecond time-scales. 

Raman spectroscopy has enjoyed a dramatic improvement during the last few years the interference by fluorescence of impurities is virtually eliminated. Up-to-date near-infrared Raman spectrometers now meet most demands for a modern analytical instrument concerning applicability, analytical information and convenience. In spite of its potential abilities, Raman spectroscopy has until recently not been extensively used for real-life polymer/additive-related problem solving, but does hold promise. Resonance Raman spectroscopy exhibits very high selectivity. Further improvements in spectropho-tometric measurement detection limits are also closely related to advances in laser technology. Apart from Raman spectroscopy, areas in which the laser is proving indispensable include molecular and fluorescence spectroscopy. The major use of lasers in analytical atomic... 

Most chemists tend to think of infrared (IR) spectroscopy as the only form of vibrational analysis for a molecular entity. In this framework, IR is typically used as an identification assay for various intermediates and final bulk drug products, and also as a quantitative technique for solution-phase studies. Full vibrational analysis of a molecule must also include Raman spectroscopy. Although IR and Raman spectroscopy are complementary techniques, widespread use of the Raman technique in pharmaceutical investigations has been limited. Before the advent of Fourier transform techniques and lasers, experimental difficulties limited the use of Raman spectroscopy. Over the last 20 years a renaissance of the Raman technique has been seen, however, due mainly to instrumentation development. 

Figure 2. Experimental set-up for Raman spectroscopy. The desired laser line is isolated from other plasma lines by a narrow bandpass filter or broadband prism monochromator, then focused onto a sample in a capillary tube. A collecting lens placed at a 90° angle to the incident beam focuses the scattered light onto the entrance slit of a monochromator with output to a photomultiplier tube (in the case of a scanning instrument) or a diode array detector.

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. 

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