Coherent Stimulated Raman Scattering

Coherent Raman scattering has several features that make it particularly applicable to microscopy [83]. First, the excitation frequencies can be chosen to image structures with particular chemical compositions. Since the selectivity depends on the difference between the two frequencies rather than their absolute values, the wavelengths required are shorter than would be needed for imaging the same vibrational modes by IR absorption, and this provides greater spatial resolution. 

12 Raman Scattering and Other Multi-photon Processes 

Because external labels are not required, the signals are not limited by bleaching of the probe as they usually are in fluorescence microscopy, nor perturbed by effects of the probe on the sample. The quadratic dependence of the signal on the intensity of the second beam, combined with the linear dependence on the intensity of the first beam, allows very tight focusing of the image. Finally, the technique can be remarkably sensitive, as shown by studies of single lipid bilayers [84-86]. 

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Unlike the typical laser source, the zero-point blackbody field is spectrally white , providing all colours, CO2, that seek out all co - CO2 = coj resonances available in a given sample. Thus all possible Raman lines can be seen with a single incident source at tOp Such multiplex capability is now found in the Class II spectroscopies where broadband excitation is obtained either by using modeless lasers, or a femtosecond pulse, which on first principles must be spectrally broad [32]. Another distinction between a coherent laser source and the blackbody radiation is that the zero-point field is spatially isotropic. By perfonuing the simple wavevector algebra for SR, we find that the scattered radiation is isotropic as well. This concept of spatial incoherence will be used to explain a certain stimulated Raman scattering event in a subsequent section. 

A light pulse of a center frequency Q impinges on an interface. Raman-active modes of nuclear motion are coherently excited via impulsive stimulated Raman scattering, when the time width of the pulse is shorter than the period of the vibration. The ultrashort light pulse has a finite frequency width related to the Fourier transformation of the time width, according to the energy-time uncertainty relation. 

Fig. 2.2. Two generation models of coherent optical phonons, (a), (c), (e) impulsive stimulated Raman scattering (ISRS). (b), (d), (f) displacive excitation of coherent phonons (DECP). Graphs (e) and (f) display the time evolution of the driving force (grey areas) and that of the displacement (solid, curves) for ISRS and DECP, respectively...

D. M. Neumark We are interested in generating coherent vibrational motion in negative ions, which typically do not have bound excited electronic states. Does your Impulsive Stimulated Raman Scattering (ISRS) scheme work if the excited state is not bound ... 

If J" —> J excitation is accompanied or followed by deexcitation J —> J" in a stimulated emission process (SEP), then the population efficiency of the level can be increased considerably. It is now known [248, 347] that the process might be made more effective by applying the A-configuration scheme in which the first-step (J" — J ) excitation pulse is applied after the second-step (J — J") pulse which, at first glance, seems surprising. This process is called stimulated Raman scattering by delayed pulses (STIRAP). The population transfer here takes place coherently and includes coordination of the Rabi nutation phase in both transitions. 

Up to now/ the dimer laser system has been described alone in terms of population inversion between suitable energy levels/ and for this description the condition S2 > A 2 is indeed the only necessary condition for cw laser oscillation/ as long as the thermal population density in the lower laser level remains negligibly low. However/ as this optically pumped laser system is a coherently excited three level system/ the coherent emission can also be described as stimulated Raman scattering/ which is resonantly enhanced by the common level 3 of the pump and laser transitions. This coupled two photon or Raman process does not require a population inversion between levels 3 and 2 and introduces qualitatively new aspects which appreciably influence and change the normal laser behaviour. For a detailed and deeper description of the coherently excited three level dimer... 

From Eq. (3.6-4) we immediately recognize that in stimulated Raman scattering processes where only one input laser field with frequency is employed, a coherent Stokes wave is generated for those Raman modes which have the highest ratio between differential Raman cross section and linewidth F. The latter corresponds to the dephasing time T2 of the physical system, F = l/Tj, and reflects the damping of the system. 

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). 

Consider a time-resolved, electronically nonresonant CARS spectrum from a molecular liquid. In the CARS process, the laser pump pulses create a linear combination (that is the inteimolecular rovibrational coherence) of Raman active rovibrational transitions between molecules at position rr and r in the mixture. This stimulated Raman scattering process is carried out by two-coincident laser pulsesfl, II) with central frequenciesfwave vectors) C0i(k ) and (Oiiikii). By applying the third pulse with C0 (kni) to the liquid after time delay t, the time dependence of the inteimolecular rovibrational coherence is detected through the measurement of the intensity of the scattered photon with kj... 

Coherent Raman spectroscopy Coherent Raman spectroscopy is a term that refers to a series of closely related nonlinear Raman techniques in which the scattered Raman radiation emerges from the sample as a coherent beam -coherent meaning that the photons are all in phase with one another. The coherent techniques include Stimulated Raman Scattering (SRS), Coherent anti-Stokes Raman Spectroscopy (CARS), Coharent Stokes Raman Spectroscopy (CSRS), and Stimulated Raman Gain Spectroscopy (SRGS). Although most of the nonlinear Raman techniques are also coherent techniques, there is one incoherent nonlinear Raman process called Hyper Raman. 

Impulsive stimulated Raman scattering (ISRS) Impulsive stimulated Raman scattering (ISRS) is the creation of coherent ground-state nuclear motion through an impulsive force caused by the interaction of a Raman-active medium with an ultrashort light pulse. 

Photoacoustic Raman spectroscopy (PARS) Photoacoustic Raman spectroscopy (PARS) is again a nonlinear spectroscopic technique. In this technique, selective population of a given energy state of a system (transitions must involve change in polarizability) is amplified using coherent Raman amplification (also known as stimulated Raman scattering). In this process, it is also important that the frequency difference of the two incident laser beams must be adjusted to equal the frequency of Raman-active transition. 

When a femtosecond laser pulse passes through nearly any medium, coherent vibrational excitation (in general, initiation of coherent wavepacket propagation) is likely [33, 34]. One- or two-photon absorption of a visible or ultraviolet pulse into an electronic excited state can result in phase-coherent motion in the excited-state potential [35]. Impulsive stimulated Raman scattering can initiate phase-coherent vibrational motion in the electronic... 

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