Laser optical vibration

Simultaneous with the publication of Hocker et al., there appeared the results of Yardley and Moore [142] on laser-excited vibrational fluorescence in CH4. A mechanically chopped He-Ne 3.39-micron laser [143, 144] was used to excite the asymmetric stretching [/ = 2948 cm-1 (36.55 X 10-2 eV)] vibration, i>3 (see Figure 3.17). The optical arrangement is shown in Figure 3.18. The He-Ne laser tube, 220 cm in length, is shown on the left. Mx, M2, and Ms are mirrors Bx and B2 are baffles to eliminate stray light Lx and L2 are lenses which focus the laser output into a collimated beam having a diameter of 2 mm, and thence, into a Pyrex fluorescence cell. At the focal point between Li and L2 is a chopper wheel, to produce a nearly perfect square wave modulated at frequencies between 600 and 10,000 Hz. An audio oscillator and a 60-W amplifier are used to drive the synchronous chopper motor. An InSb infrared detector (response time of about 4 nsec) is used to... 

Since it is estimated that the vibrational temperatures Tn and T2 can reach several thousand degrees, the population of vibrationally excited molecules becomes significant in typical laser discharges. Furthermore, the vibrational populations are strongly influenced by the extraction of laser optical power from the discharge. Therefore, it is expected that the electron kinetics will be influenced not only by the presence of vibrationally excited molecules in the discharge, but that these kinetics will also be a function of the operating conditions of the laser. 

Figure 4.10 (Top) Schematic diagram of a Michelson interferometer. ZPD stands tor zero path length difference (i.e., the fixed mirror and moving mirror are equidistant from the beam splitter). (From Coates, J., Vibrational spectroscopy, in Ewing, G.W., ed.. Analytical Instrumentation Handbook, 2nd edn., Marcel Dekker, Inc., New York, 1997. With permission.) (Bottom) A simple commercial FTIR spectrometer layout showing the He-Ne laser, optics, the source. Interferometer, sample, and detector. ( Thermo Fisher Scientific (www.thermotisher.com). Used with permission.)...

Chemical analysis of polymers typically deals with monomers or functional groups rather than constituent atoms. Thermal infrared and laser optical Raman spectrometry are the typical tools (36) (see Test Methods Vibrational Spectroscopy), but frequently, specific specimen size or form is required. For physical properties, mechanical and sonic/ultrasonic NDT methods are available (see above). Molecular mass distribution and related properties of polymers, or fiber or particle volume fraction and distribution for PMC, are usually determined destructively (see Test Methods). 

Raman Spectroscopy. Fortunately an alternate solution to identification is offered by Raman spectroscopy. This laser-optical technique can determine with great accuracy the bonding states of the carbon atoms (sp for graphite or sp for diamond) by displaying their vibrationcil properties.f l The Raman spectra is the result of the inelastic scattering of optical photons by lattice vibration phonons. 

See also Fourier Transformation and Sampling Theory FT-Raman Spectroscopy, Applications Gas Phase Applications of NMR Spectroscopy High Resolution IR Spectroscopy (Gas Phase), Applications Hydrogen Bonding and Other Physicochemical Interactions Studied By IR and Raman Spectroscopy Laboratory Information Management Systems (LIMS) Laser Spectroscopy Theory Light Sources and Optics Vibrational, Rotational and Raman Spectroscopy, Historical Perspective. 

Light sources can either be broadband, such as a Globar, a Nemst glower, an incandescent wire or mercury arc lamp or they can be tunable, such as a laser or optical parametric oscillator (OPO). In the fomier case, a monocln-omator is needed to achieve spectral resolution. In the case of a tunable light source, the spectral resolution is detemiined by the linewidth of the source itself In either case, the spectral coverage of the light source imposes limits on the vibrational frequencies that can be measured. Of course, limitations on the dispersing element and detector also affect the overall spectral response of the spectrometer. 

Many of the fiindamental physical and chemical processes at surfaces and interfaces occur on extremely fast time scales. For example, atomic and molecular motions take place on time scales as short as 100 fs, while surface electronic states may have lifetimes as short as 10 fs. With the dramatic recent advances in laser tecluiology, however, such time scales have become increasingly accessible. Surface nonlinear optics provides an attractive approach to capture such events directly in the time domain. Some examples of application of the method include probing the dynamics of melting on the time scale of phonon vibrations [82], photoisomerization of molecules [88], molecular dynamics of adsorbates [89, 90], interfacial solvent dynamics [91], transient band-flattening in semiconductors [92] and laser-induced desorption [93]. A review article discussing such time-resolved studies in metals can be found in... 

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. 

Optical metiiods, in both bulb and beam expermrents, have been employed to detemiine tlie relative populations of individual internal quantum states of products of chemical reactions. Most connnonly, such methods employ a transition to an excited electronic, rather than vibrational, level of tlie molecule. Molecular electronic transitions occur in the visible and ultraviolet, and detection of emission in these spectral regions can be accomplished much more sensitively than in the infrared, where vibrational transitions occur. In addition to their use in the study of collisional reaction dynamics, laser spectroscopic methods have been widely applied for the measurement of temperature and species concentrations in many different kinds of reaction media, including combustion media [31] and atmospheric chemistry [32]. 

The most widely employed optical method for the study of chemical reaction dynamics has been laser-induced fluorescence. This detection scheme is schematically illustrated in the left-hand side of figure B2.3.8. A tunable laser is scanned tlnough an electronic band system of the molecule, while the fluorescence emission is detected. This maps out an action spectrum that can be used to detemiine the relative concentrations of the various vibration-rotation levels of the molecule. 

Schematic diagrams of modem experimental apparatus used for IR pump-probe by Payer and co-workers [50] and for IR-Raman experiments by Dlott and co-workers [39] are shown in figure C3.5.3. Ultrafast mid-IR pulse generation by optical parametric amplification (OPA) [71] will not discussed here. Single-colour IR pump-probe or vibrational echo experiments have been perfonned with OP As or free-electron lasers. Free-electron lasers use...

---