Coherent Raman excitation

Vibrationally excited hydrogen (v = 1) cannot be produced by direct photon absorption, but may be produced by coherent Raman excitation... 

Figure 6.1 Nonlinear optical responses, (a) Second-order SF generation, the transition probability is enhanced when the IR light is resonant to the transition from the ground state g to a vibrational excited state V. CO is the angular frequency of the vibration, (b) Third-order coherent Raman scheme, the vibrational coherence is generated via impulsive stimulated...

Raman excitation. and I2s are the high-frequency and low-frequency components of the pump light pulse. A probe pulse of frequency 12 interacts with the coherence to present the optical response of the fundamental frequency 12 + C0fsl2. (c) Fourth-order coherent Raman scattering, the optical response of the second harmonic frequency 212 + co 2I2 is modulated by the vibrational coherence. 

In the current chapter, the principles of Raman excitation and interface-selective detection of vibrational coherence are described, including applications to air/liquid, liquid/liquid, air/solid interfaces, and an organic submonolayer. 

Figure 1 Schematic representation of a time-resolved coherent Raman experiment, (a) The excitation of the vibrational level is accomplished by a two-photon process the laser (L) and Stokes (S) photons are represented by vertical arrows. The wave vectors of the two pump fields determine the wave vector of the coherent excitation, kv. (b) At a later time the coherent probing process involving again two photons takes place the probe pulse and the anti-Stokes scattering are denoted by subscripts P and A, respectively. The scattering signal emitted under phase-matching conditions is a measure of the coherent excitation at the probing time, (c) Four-photon interaction scheme for the generation of coherent anti-Stokes Raman scattering of the vibrational transition.

In impulsive multidimensional (1VD) Raman spectroscopy a sample is excited by a train of N pairs of optical pulses, which prepare a wavepacket of quantum states. This wavepacket is probed by the scattering of the probe pulse. The electronically off-resonant pulses interact with the electronic polarizability, which depends parametrically on the vibrational coordinates (19), and the signal is related to the 2N + I order nonlinear response (18). Seventh-order three-dimensional (3D) coherent Raman scattering, technique has been proposed by Loring and Mukamel (20) and reported in Refs. 12 and 21. Fifth-order two-dimensional (2D) Raman spectroscopy, proposed later by Tanimura and Mukamel (22), had triggered extensive experimental (23-28) and theoretical (13,25,29-38) activity. Raman techniques have been reviewed recently (12,13) and will not be discussed here. 

An alternate approach is to perform coherent Raman spectroscopy in the time domain rather than in the frequency domain. In this case, a single laser that produces short pulses with sufficient bandwidth to excite all of the Raman modes of interest is employed. One pulse or one pair of time-coincident pulses is used to initiate coherent motion of the intermolecular modes. The time dependence of this coherence is then monitored by another laser pulse, whose timing can be varied to map out the Raman free-induction decay (FID). It should be stressed at this point that the information contained in the Raman FID is identical to that in a low-frequency Raman spectrum and that the two types of data can be interconverted by a straightforward Fourier-transform procedure (12-14). Thus, whether a frequency-domain or a time-domain coherent Raman technique should be employed to study a particular system depends only on practical experimental considerations. 

From an experimental point of view, it is quite evident that for the four nonlinear coherent Raman techniques discussed until now, one either measures the radiation generated at anti-Stokes frequency (CARS, ll)as = 2ui-cvs) or at Stokes frequency (CSRS, 2cJs - or one determines the change AS in the laser beam power (o/ z, IRS uJs -SRGS). In order to get full Raman information of the medium, it is necessary to tune the frequency difference ojl-ujs, then, successively all Raman-active vibrations (or rotations, or rotation-vibrations) will be excited and a complete nonlinear Raman spectrum is then obtained. 

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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