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In the present work, we analyze the influence of the polarization effects taking place during the course of a 2DIR spectroscopy experiment performed on a molecular system undergoing an intermolecular vibrational energy transfer process. When both donor and acceptor molecules participating in the vibrational energy transfer are embedded in a host solvent, they face rotational diffusion that strongly distorts the resulting 2DIR spectra. It could be expected that the difference between rotational diffusion constants will be of particular interest. For this purpose, the polarization effects are discussed according to the different orderings of the laser‐molecule interactions. Next, we study the distortions of the spectra as a function of the rotational diffusion constants of the individual molecules. The knowledge of these polarization effects is relevant to the interpretation of the spectra. Finally, the conclusions reached in this work for a vibrational energy transfer are valid for any other type of third‐order optical process performed on the same molecular system. [ABSTRACT FROM AUTHOR]

In the present work, the analytic description of an intermolecular vibrational energy transfer, analyzed by two-dimensional infrared spectroscopy, is established. The energy transfer process takes place between the dark combination states of low frequency modes pertaining to different molecules. The appearance of the cross-peaks results from coherent transfer between these combination states and optically active states of the molecule. Such a process has recently been observed experimentally between the nitrile groups of acetonitrile- d3 and benzonitrile molecules. This molecular system will be used as a model for the simulations of their two-dimensional infrared spectra. The dependence of the cross-peak growth, which is a signature of the intermolecular energy transfer, will be discussed in detail as a function of the molecular dynamical constants. [ABSTRACT FROM AUTHOR]