Two-dimensional electronic–vibrational spectroscopy: Exploring the interplay of electrons and nuclei in excited state molecular dynamics

Two-dimensional electronic–vibrational spectroscopy (2DEVS) is an emerging spectroscopic technique which exploits two different frequency ranges for the excitation (visible) and detection (infrared) axes of a 2D spectrum. In contrast to degenerate techniques, such as electronic or infrared spectroscopy, spectral features 2DEV spectrum report cross correlations between fluctuating vibrational energy gaps rather than autocorrelations in spectroscopies. The center line slope reports on this correlation function directly can reveal specific couplings rapid changes structure, example. involvement types transition moments, visible infrared, makes 2DEVS very sensitive vibronic mixing. spectra also feature improved resolution, making method valuable unraveling highly congested molecular complexes. unique are illustrated paper with examples their origin described at intuitive level references formal derivations provided. Although early its development far from fully explored, has already proven be addition tool box ultrafast nonlinear optical promising potential future efforts explore intricate connection nuclear degrees freedom charge transport applications.