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Three-dimensional-IR spectroscopy: Beyond the two-point frequency fluctuation correlation function
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Three-dimensional-IR spectroscopy is proposed as a new spectroscopic technique that is sensitive to three-point frequency fluctuation correlation functions. This will be important when the statistics of the underlying stochastic process is non-Gaussian, and hence when the system does not follow the linear response hypothesis. Furthermore, a very general classification of nonlinear spectroscopy in terms of higher order frequency fluctuation correlation functions is introduced, according to which certain moments of a multidimensional spectrum are related to certain frequency fluctuation correlation functions. The classification is rigorous in the so-called inhomogenous limit, but remains valid approximately also when motional narrowing becomes important. The work also puts a recent paper [J. Bredenbeck et al., Phys. Rev. Lett.95, 083201 (2005)] onto solid theoretical grounds, where we have shown for the first time that fifth-order spectroscopy—in this case transient two-dimensional spectroscopy—is indeed sensitive to the three-point frequency fluctuation correlation function.
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