Inverse Raman spectroscopy

Rahn L. A., Palmer R. E. Studies of nitrogen self-broadening at high temperature with inverse Raman spectroscopy, J. Opt. Soc. Am. B 3, 1164-9 (1986). 

D. R. Crosley and M. A. Schroeder, Development of Inverse Raman Spectroscopy for Probing Rapidly Decomposing Explosives and Propellants, ARBRL-TR-02345, Ballistic Res. Lab., Army Armament Res. Dev. Command, Aberdeen Proving Ground, MD, USA (1981). 

Figure 3.6-4 Schematic diagram for a few techniques in nonlinear (coherent) Raman spectroscopy (CSRS Coherent Stokes Raman Spectroscopy SRGS Stimulated Raman Gain Spectroscopy IRS Inverse Raman Spectroscopy (= SRLS Stimulated Raman Loss Spectroscopy) CARS Coherent anti-Stokes Raman Spectroscopy PARS Photoacoustic Raman Spectroscopy).

Stimulated Raman gain and inverse Raman spectroscopy (SRGS, IRS)... 

Figure 3.6-14 Schematic for qua.si-cw inverse Raman spectroscopy (Owyoung, 1978).

In this section mainly results of linear Raman spectroscopy of gases and vapours have been considered and selected examples of the results of nonlinear techniques were included, e.g. CARS or stimulated and inverse Raman spectroscopy, by which much higher resolution can be achieved. Further such investigations have been reviewed elsewhere (Esherick and Owyoung, 1982 Schrotter et al., 1988a, 1988b, 1990 Lavorel et al., 1992). 

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). 

The advantages of the two coherent Raman techniques, stimulated Raman gain (SRGS) and inverse Raman spectroscopy (IRS), have been described in detail in Secs. 3.6.1.3 and 3.6.2.3. Here, we present an instructive example for each technique emphasizing the high resolution capability of the.se methods. 

Schrotter HW, Frunder H, Berger H, Boquillon JP, Lavorel B, Millot G (1988) High Resolution CARS and Inverse Raman Spectroscopy. In Clark RJH, Hester RE (eds) Advances in Nonlinear Spectroscopy, vol 15, Wiley, Chiche.ster, p 97 Schrotter HW, Klockner HW (1979) In Weber A (ed) Topics in Current Physics, vol 11, Springer Verlag, Berlin Heidelberg New York... 

Inverse Raman spectroscopy The Inverse Raman effect is a form of Raman scattering, first noted by W.J. Jones and B.P. Stoicheff, wherein stokes scattering can exceed anti-Stokes scattering resulting in an absorption line (a dip in intensity) at the sum of irradiated monochromatic light and Raman frequency of the material. This phenomenon is referred to as the inverse Raman Effect, application of the phenomenon is referred to as inverse Raman spectroscopy, and a record of the continuum is referred to as an inverse Raman spectrum. 

Modulation techniques have been shown to be capable of increasing the signal-to-noise ratio for Raman spectroscopy, this being illustrated for the resonance-enhanced inverse Raman effect.Inverse Raman spectroscopy enables spectra of highly luminescent systems to be recorded. A suitable spectrometer has been described in which a resolution of 1 cm was achieved with scan rates dependent only upon the scan speed of the dye laser used for excitation.A 100-fold increased sensitivity was reported with the use of a multiplex spectrometer for... 

In the previous subsections we briefly introduced some nonlinear techniques of Raman spectroscopy. Besides stimulated Raman spectroscopy, Raman gain spectroscopy, inverse Raman spectroscopy, and CARS, several other special techniques such as the Raman-induced Kerr effect [361] or coherent Raman ellipsometry [362] also offer attractive alternatives to conventional Raman spectroscopy. 

H.W. Schrbtter, H. Frunder, H. Berger, J.R BoquiUon, B. Lavorel, G. Millet, High resolution CARS and inverse Raman spectroscopy, mAdv. Nonlinear Spectroscopy, vol. 3 (WUey, New York, 1987), p. 97... 

In the first part of this chapter the experimental techniques of linear and nonlinear Raman spectroscopy of gases are reviewed. The nonlinear techniques (Stimulated Raman Gain Spectroscopy, Inverse Raman Spectroscopy, Coherent Anti-Stokes Raman Spectroscopy, Photo-Acoustic Raman Spectroscopy, and Ionization-Detected Stimulated Raman Spectroscopy) have the capability of very high resolution, limited by the linewidths of the lasers used and pressure broadening effects. 

Fig. 7 Raman gain = stimulated Raman gain spectroscopy (SRGS), inverse Raman = inverse Raman spectroscopy (IRS) or stimulated Raman loss spectroscopy (SRLS), coherent anti-Stokes Raman spectroscopy (CARS), photoacoustic Raman spectroscopy (PARS), or ionization-detected stimulated Raman spectroscopy (IDSRS). In the following sections, the various methods are briefly described. More detailed information can be found in books [59-61], reviews [45,46,57,58,62,63] and conference reports [64-73].

I. Stimulated Raman Gain and Inverse Raman Spectroscopy... 

Band contours in the spontaneous Raman spectra of a number of five-atomic spherical top molecules were investigated [242-245], The rotational structure in the Q branch of the Pi fundamental of CF4 was resolved by inverse Raman spectroscopy [246,247]. 

Ethylene has a center of symmetry and no dipole moment and, therefore, the Raman spectrum is an important source of structural information. After the early work on the rotational [269] and rovibrational Raman spectrum [270], these spectra were thoroughly studied in a series of publications [271-273]. Overtones and combination bands were measured in an intracavity Raman experiment by Knippers et al. [274]. The Q branch of the V2 band was resolved by pulsed CARS spectroscopy in a molecular beam experiment [275] and the band by inverse Raman spectroscopy [90]. 

HW Schrotter, H Frunder, H Berger, JP Boquillon, B Lavorel, G Millot. High resolution CARS and inverse Raman spectroscopy. In RJH Clark, RE Hester, eds. Advances in Non-hnear Spectroscopy Vol. 15. Chichester Wiley, 1988, pp 97-147. 

JJ Valentini, P Esherick, A Owyoung. Use of a free-expansion jet in Ultra-high-resolution inverse Raman spectroscopy. Chem Phys Lett 75 590-592, 1980. 

RS McDowell, CW Patterson, A Owyoung. Quasi-cw inverse Raman spectroscopy of the Pi fundamental of CH4. J Chem Phys 72 1071-1076, 1980. 

A Owyoung, P Esherick, AG Robiette, RS McDowell. High-resolution inverse Raman spectroscopy of the p, band of "SiH4. J Mol Spectrosc 86 209-215, 1981. 

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