Applications of nonlinear Raman spectroscopy

The methods of nonlinear Raman spectroscopy, i. e. spontaneous hyper Raman scattering (based on the hyperpolarizability) and coherent nonlinear Raman scattering (based on the third-order-nonlinear susceptibilities) are discussed in detail in Sec. 3.6.1. In Sec. 3.6.2 the instrumentation needed for these types of nonlinear spectroscopy is described. In this section we present some selected, typical examples of hyper Raman scattering (Sec. 6.1.4.1), coherent anti-Stokes Raman. scattering (Sec. 6.1.4.2), stimulated Raman gain and inverse Raman spectroscopy (Sec. 6.1.4.3), photoacoustic Raman spectroscopy (Sec. 6.1.4.4) and ionization detected stimulated Raman spectroscopy (Sec. 6.1.4.5). 

---

A. B. Harvey, ed., Chemical Applications of Nonlinear Raman Spectroscopy, p. 1. Academic Press, New York, 1981. 

In this section we first give a survey on the most common nonlinear Raman processes, i. e. the (incoherent) hyper Raman scattering and several forms of coherent nonlinear Raman scattering. We then describe the instrumentation needed to perform several practical kinds of these nonlinear laser spectroscopies. Applications of nonlinear Raman spectroscopy will be found in Sec. 6.1. 

Hartke B, Kiefer W, Kolba E, Manz J, Strempel J (1992) J Chem Phys 96 5636 Hartland GV. Henson BE, Connell LL, Corcoran TC, Fclker PM (1988) J Phys Chem 92 6877 Hartland GV, Henson BE, Venture VA, Hertz RA, Felker PM (1990) J Opt Soc Am B7 1950 Hartland GV, Joireman PW, Connell LL, Felker (1992) J Chem Phys 96 179 Hartman KA, Clayton NW, Thomas GJ Jr (1973) Biochem Biophys Res Comm 50 942 Harvey AB (1981) Chemical Applications of Nonlinear Raman Spectroscopy, Academic Press, New York... 

Eckbreth, A. G., and Schreiber, P. W. "Coherent Anti-Stokes Raman Spectroscopy (CARS) Application to Combustion and Gas-Phase Diagnostics." Chemical Applications of Nonlinear Raman Spectroscopy in Laser Applications, Vol. 1. New York Academic Press, 1981. 

PM Felker, BF Henson, VA Venturo, GV Hartland. Applications of nonlinear Raman spectroscopy to molecular beam studies. In W Kiefer, M Cardona, G Schaack, FW Schneider, HW Schrotter, eds. Proceedings of the Xlllth International Conference on Raman Spectroscopy. Chichester Wiley, 1992, pp 230-231. 

Figure 16 The pure rotational photoacoustic Raman (PARS) spectrum of CO2 gas at a pressure of 80 kPa (600 torr) pump laser wave length at 532 nm. Note the complete absence of any acoustical signal due to Rayleigh scattering (at 532 nm). Reproduced by permission of Academic Press from Barrett JJ (1981) Photoacoustic Raman Spectroscopy. In Harvey AB (ed) Chemical Applications of Nonlinear Raman Spectroscopy, pp 89-169. New York Academic Press.

Ichimura, T., Hayazawa, N., Hashimoto, M., Inouye, Y, and Kawata, S. 2004b. Application of tip-enhanced microscopy for nonlinear Raman spectroscopy. Appl. Phys. Lett. 84 1768-70. 

This chapter describes the application of these techniques to a liquid photolytic reaction. The motivation was the assessment of the capabilities and limitations of single-pulse nonlinear Raman spectroscopy as a probe of fast reactions in energetic materials. 

Nonlinear vibrational spectroscopy provides accessibility to a range of vibrational information that is hardly obtainable from conventional linear spectroscopy. Recent progress in the pulsed laser technology has made the nonlinear Raman effect a widely applicable analytical method. In this chapter, two types of nonlinear Raman techniques, hyper-Raman scattering (HRS) spectroscopy and time-frequency two-dimensional broadband coherent anti-Stokes Raman scattering (2D-CARS) spectroscopy, are applied for characterizing carbon nanomaterials. The former is used as an alternative for IR spectroscopy. The latter is useful for studying dynamics of nanomaterials. 

Ichimura T, Hayazawa N, Hashimoto M, Inouye Y, Kawata S (2004) Application of tip-enhanced microscopy for nonlinear Raman spectroscopy. Appl Phys Lett 84 1768 Ichimura T, Hayazawa N, Hashimoto M, Inouye Y, Kawata S (2004) Tip-enhanced coherent anti-stokes raman scattering for vibrational nanoimaging. Phys Rev Lett 92 220801 Tanaka S, Maeda Y, Cai L, Tabata H, Kawai T (2001) Application of tip-enhanced microscopy for nonlinear Raman spectroscopy. Jpn J Appl Phys 40 4217 Watanabe H, Ishida Y, Hayazawa N, Inouye Y, Kawata S (2004) Tip-enhanced near-field Raman analysis of tip-pressurized adenine molecule. Phys Rev B 69 155418 Yano T, Verma P, Saito Y, Ichimura T, Kawata S (2009) Pressure-assisted tip-enhanced Raman imaging at a resolution of a few nanometres. Nature Photon 3 473 Yano T, Inouye Y, Kawata S (2006) Nanoscale uniaxial pressure effect of a carbon nanotube bundle on tip-enhanced near-field Raman spectra. Nano Lett 6 1269 Downes A, Salter D, Elfick A (2006) Heating effects in tip-enhanced optical microscopy. Opt Exp 14 5216... 

Nonlinear techniques have been used to overeome some of the drawbacks of conventional Raman spectroscopy, particularly its low dficienev, its limitation to the visible and near-ultraviolet regions, and its susceptibility to interference from fluorescence. A major disadvantage of nonlinear methods is that they lend to be analyte specific and often require several different tunable lasers to be applicable lo diverse species. I o dale, none of the nonlinear methods has found widespread application among nonspccialisls. However, many of these methods have shown considerable promise. As less expensive and more routinely useful lasers become available, nonlinear Raman methods, particu-larlv CARS, should become more widely used. 

In these lectures I have presented a survey of modern Raman spectroscopy, emphasising the applications to gases. Since it is necessary to have some idea of the theory in order to fully appreciate the various applications, I have outlined the semi-classical theory of both conventional and nonlinear Raman processes. Quite a lot of space is devoted to the basis of conventional Raman scattering, not only because it provides an essential foundation for the semi-classical theory of nonlinear processes, but also to emphasise that, using modern electro-optical technology, conventional Raman is still very much the preferred technique for many applications, and that the new nonlinear techniques should only be used when conventional Raman fails or when very high resolution is essential. 

In this section we briefly discuss some special techniques of linear and nonlinear Raman spectroscopy that have particular advantages for different applications. These are the resonance Raman effect, surface-enhanced Raman signals, Raman microscopy, and time-resolved Raman spectroscopy. 

W. Kiefer, Nonlinear Raman spectroscopy applications, in Encyclopedia of Spectroscopy and Spectrometry (Academic Press, New York, 2000), p. 1609... 

Matrix Isolation Studies By IR and Raman Spectroscopies Medical Science Applications of IR Microwave and Radiowave Spectroscopy, Applications Nonlinear Raman Spectroscopy,... 

Applications of spontaneous nonlinear Raman spectroscopy (Hyper-Raman scattering)... 

See also Atomic Absorption, Theory IR Spectroscopy, Theory Nonlinear Raman Spectroscopy, Applications Nonlinear Raman Spectroscopy, Instruments Nonlinear Raman Spectroscopy, Theory Rotational Spectroscopy, Theory Symmetry in Spectroscopy, Effects of Vibrational, Rotational and Raman Spectroscopy, Historical Perspective. 

With the available high-power lasers the nonlinear response of matter to incident radiation can be studied. We will briefly discuss as examples the stimulated Raman effect, which can be used to investigate induced vibrational and rotational Raman spectra in solids, liquids or gases, and the inverse Raman effect which allows rapid analysis of a total Raman spectrum. A review of the applications of these and other nonlinear effects to Raman spectroscopy has been given by Schrotter2i4)... 

---