Stokes, transitions energy level

Fig. 2 Jablonski energy level diagram illustrating possible transitions, where solid lines represent absorption processes and dotted lines represent scattering processes. Key A, IR absorption B, near-IR absorption of an overtone C, Rayleigh scattering D, Stokes Raman transition and E, anti-Stokes Raman transition. S0 is the singlet ground state, S, the lowest singlet excited state, and v represents vibrational energy levels within each electronic state.

As already introduced in section I of this chapter, in a CARS process (Figures 7.9a-c see also Figure 7.1c), a Raman transition between two vibrational energy levels of a molecule is coherently driven by two optical laser fields (frequencies co and co) and subsequently probed by interaction with a third field at frequency co, . This generates the anti-Stokes signal at the blue-shifted frequency cars = p- The... 

Because of the Stokes shift for vibrationally relaxed systems (the rate of transfer < the rate of vibrational relaxation), transfer between like molecules is less efficient than that between unlike molecules when acceptor is at a lower energy level (exothermic transfer). No transfer is expected if the acceptor level is higher than the donor level. If (i) the acceptor transition is strong (Emaz —- 10,000), (ii) there is significant spectral overlap, and (iii) the donor emission yields lie within 0.1 — 1.0, then R0 values of 50-100 A are predicted. 

Figure 3-43 Schematic representation of the photoacoustic Raman scattering (PARS) process, (a) A simple energy level diagram illustrating the Raman interaction that occurs in the PARS process, (b) Basic elements of the PARS experimental arrangement. The pump beam is attenuated and the Stokes beam is amplified by the stimulated Raman process that takes place where the beams overlap in the gas sample cell. For each Stokes photon created by the Raman process, one molecule is transferred from the lower state to the upper state of the transition. Collisional relaxation of these excited molecules produces a pressure change that is detected by a microphone. (Reproduced with permission from Ref. 107.)...

Raman Selection Rules. For polyatomic molecules a number of Stokes Raman bands are observed, each corresponding to an allowed transition between two vibrational energy levels of the molecule. (An allowed transition is one for which the intensity is not uniquely zero owing to symmetry.) As in the case of infrared spectroscopy (see Exp. 38), only the fundamental transitions (corresponding to frequencies v, V2, v, ...) are usually intense enough to be observed, although weak overtone and combination Raman bands are sometimes detected. For molecules with appreciable symmetry, some fundamental transitions may be absent in the Raman and/or infrared spectra. The essential requirement is that the transition moment F (whose square determines the intensity) be nonzero i.e.. 

Fig. 10. Energy level diagram for electronic resonance enhancement in the CARS spectrum of hydroxyl, OH, in which the pump laser is tuned into resonance. Strong enhancement occurs only for allowed downward Stokes transitions leading to a triplet spectrum.

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