Over the past ten years, the techniques and sophistication of analysis of ultrafast spectroscopy have advanced to a remarkable extent. Following the demonstration and validation of new methods using simple dilute dye solutions, many applications of these new techniques have been to photosynthetic systems. The reasons for this are not hard to find: photosynthetic pigment protein complexes function through a delicate interplay of interpigment and pigment-environment interactions, and standard methods provide an unsatisfactory level of microscopic insight because signals are dominated by inhomogeneous effects, or the methods themselves are insensitive to the interactions between states of interest. The developments described in this chapter are designed to address all these issues. Multiphoton transient absorption spectroscopy helps to unravel complex energy transfer and relaxation pathways. Two-photon excitation spectroscopy prepares states that are not ac cessible directly from the ground state. Photon echo methods defeat inhomogeneous broadening, measure it, and exploit it to observe energy transfer between chemically identical donors and acceptors. Two-dimensional techniques explicitly reveal electronic couplings and the pathways of energy flow. New methods based on Raman spectroscopy reveal vibrational frequencies in excited states, and indeed a wide range of transient species.
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Zigmantas, D., Ma, YZ., Read, E.L., Fleming, G.R. (2008). Nonlinear Femtosecond Optical Spectroscopy Techniques in Photosynthesis. In: Aartsma, T.J., Matysik, J. (eds) Biophysical Techniques in Photosynthesis. Advances in Photosynthesis and Respiration, vol 26. Springer, Dordrecht. https://doi.org/10.1007/978-1-4020-8250-4_11
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