2D-Raman

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. 

Figure 5 Simulations of the 2D Raman spectrum for the Brownian oscillators in Fig. 4, CCI4, for nonlinear polarizability coupling [Equation (21)] in the (a) fully uncoupled, = <5,j, and (b) fully coupled, = 1, limits.

Figure 6 Simulations of the 2D Raman spectrum for the anharmonically (fully) coupled v and v4 modes [Equation (20)]. (a) The coupled response, (b) The g44 coupled response.

Koehl RM, Adachi S, Nelson KA. Multiple-pulse control and bispectral 2D Raman analysis of nonlinear lattice dynamics. In Ultrafast Phenomena XI. T Elsaesser et al., eds. Berlin Springer-Verlag, 1998 136-137. 

Finally we note several future directions which should be studied (a) Our final results for the VER rate depend on a width parameter y. Unfortunately we do not know which value is the most appropriate for y. Nonequilibrium simulations (with some quantum corrections [39]) might help this situation, and they are useful to investigate energy pathways or sequential IVR (intramolecular vibrational energy redistribution) [40] in a protein, (b) This work is motivated by pioneering spectroscopic experiments by Romesberg s group. The calculation of the VER rate and the linear or nonlinear response functions, related to absorption or 2D-IR (or 2D-Raman) spectra [41—44], is desirable, (c)... 

The authors stress the advantages of pre-resonance intensity enhancement effect accompanying the FT-Raman measurements allowing to detect carotenoids even in trace amounts with simultaneous elimination of background fluorescence of the plant sample. These special advantages of FT-Raman spectroscopy applied to 2D Raman mappings enabled to illustrate the distribution of individual plant carotenoids independently from each other in the same sample [4]. Furthermore, the high potential of FT-Raman microspectroscopy to obtain detailed information about microstructure and chemical composition of fennel fruits, chamomile inflorescence, and curcuma roots was demonstrated [11]. 

Figure 10.7 Composite specimen under four-point bending. Variation of the 2D Raman peak position with tensile strain for SWCNTs dispersed in epoxy resin. Reprinted with permission from Ref [84].

Choi HC, Jung YM, Noda 1, Kim SB (2003) A study of the mechanism of the electrochemical reaction of Utfaium with CoO by two-dimensional soft X-ray absorption spectroscopy (2D XAS), 2D Raman, and 2D heterospectral XAS-Ramtm correlation analysis. J Phys Chem B 107(24) 5806-5811. doi 10.1021/jp(B0438w... 

Fig. 1.5 2D Raman signal intensity of a Morse potential with linear polarizability in the strong damping case T is temperature in Kelvin [33], Reprinted from [33]. Copyright 1998, with permission from Elsevier...

Okumura, K, Tanimura, Y. (1997). Interplay of inhomogeneity and an-harmonicity in 2D Raman spectroscopy of liquids. Chem. Phys. Lett. 277 159-166. 

In this book, we collect a series of chapters dedicated to the state-of-art studies of optical spectroscopy in the time domain on complex liquids of different nature. In Chap. 1, a new nonlinear spectroscopic technique, 2D-Raman, is comprehensively reviewed. This is probably tbe most promising experimental tool able to collect truly new information on fast dynamics in liquid matter. Chapter 2 is dedicated to optical Kerr effect techniques and to the investigation of relaxation d5mamics in complex liquids, inclusive of relative slow collective... 

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