Hyper-Raman scattering spectroscopy

Cho M 1997 Off-resonant coherent hyper-Raman scattering spectroscopy J. Chem. Phys. 106 7550-7... 

Similarly, the first-order expansion of the p° and a of Eq. (5.1) is, respectively, responsible for IR absorption and Raman scattering. According to the parity, one can easily understand that selection mles for hyper-Raman scattering are rather similar to those for IR [17,18]. Moreover, some of the silent modes, which are IR- and Raman-inactive vibrational modes, can be allowed in hyper-Raman scattering because of the nonlinearity. Incidentally, hyper-Raman-active modes and Raman-active modes are mutually exclusive in centrosymmetric molecules. Similar to Raman spectroscopy, hyper-Raman spectroscopy is feasible by visible excitation. Therefore, hyper-Raman spectroscopy can, in principle, be used as an alternative for IR spectroscopy, especially in IR-opaque media such as an aqueous solution [103]. Moreover, its spatial resolution, caused by the diffraction limit, is expected to be much better than IR microscopy. 

Ina similarmarmerto surface-enhanced Raman scattering, surface-enhancement of hyper-Raman scattering is a promising method to study adsorbed molecules on metal surfaces [24]. Based on recent developments in plasmonics, design and fabrication of metal substrates with high enhancement activities is now becoming possible [21]. Combination of the surface enhancement with the electronic resonances would also be helpful for the practical use of hyper-Raman spectroscopy. Development of enhanced hyper-Raman spectroscopy is awaited for the study of solid/liquid interfaces. 

Here we have described two second-order non-linear spectroscopies, SFG in detail and hyper-Raman scattering briefly. 

Kneipp, J., Kneipp, H. and Kneipp, K (2006) Two-photon vibrational spectroscopy for hiosdences based on surface-enhanced hyper-Raman scattering. Proc. Natl. Acad. Sci. U.S.A., 103, 17149-17153. 

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. 

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). 

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. 

CaTi03-based solid solutions, such as CaTi03-MM 03, where M = Sr, M = Ti M = Ca, M = Zr M = Nd, M = Al M = La, M = Ga, were studied by Raman spectroscopy.48 Hyper-Raman scattering by SrTi(18Ox16Oi x)3 single crystals led to the observation of the Raman-inactive eu mode.49 Raman spectroscopy showed the absence of phase transitions in the range 5-325 K... 

Surface Enhanced Hyper-Raman Spectroscopy (SEHRS) Hyper-Raman scattering is a nonlinear three-photon energy conversion process, that offers complementary informahon to Raman spectroscopy and has some advantages... 

The main interest in hyper-Raman spectroscopy is that certain vibrational modes that are inactive in both the infrared and in conventional Raman can be active in the hyper-Raman. A good example is thetorsional mode of ethylene. Unfortunately, hyper-Raman scattering is many orders of magnitude less intense than conventional Raman, so measurements take a long time and sensitivity can be low. Gas-phase studies are therefore unfavourable, and only a few gases have been studied so far, giving just vibrational spectra at modest resolution. 

The primary object of Raman spectroscopy is the determination of molecular energy levels and transition probabilities connected with molecular transitions that are not accessible to infrared spectroscopy. Linear laser Raman spectroscopy, CARS, and hyper-Raman scattering have very successfully collected many spectroscopic data that could not have been obtained with other techniques. Besides these basic applications to molecular spectroscopy there are, however, a number of scientific and technical applications of Raman spectroscopy to other fields, which have become feasible with the new methods discussed in the previous sections. We can give only a few examples. 

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

Hyper-Raman spectroscopy is not a surface-specific technique while SFG vibrational spectroscopy can selectively probe surfaces and interfaces, although both methods are based on the second-order nonlinear process. The vibrational SFG is a combination process of IR absorption and Raman scattering and, hence, only accessible to IR/Raman-active modes, which appear only in non-centrosymmetric molecules. Conversely, the hyper-Raman process does not require such broken centrosymmetry. Energy diagrams for IR, Raman, hyper-Raman, and vibrational SFG processes are summarized in Figure 5.17. 

Here, E is the strength of the applied electric field (laser beam), a the polarizability and / and y the first and second hyper-polarizabilities, respectively. In the case of conventional Raman spectroscopy with CW lasers (E, 104 V cm-1), the contributions of the / and y terms to P are insignificant since a fi y. Their contributions become significant, however, when the sample is irradiated with extremely strong laser pulses ( 109 V cm-1) created by Q-switched ruby or Nd-YAG lasers (10-100 MW peak power). These giant pulses lead to novel spectroscopic phenomena such as the hyper-Raman effect, stimulated Raman effect, inverse Raman effect, coherent anti-Stokes Raman scattering (CARS), and photoacoustic Raman spectroscopy (PARS). Figure 3-40 shows transition schemes involved in each type of nonlinear Raman spectroscopy. (See Refs. 104-110.)... 

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