@unpublished{LambertVoelkerKochetal.2015, author = {Lambert, Christoph and V{\"o}lker, Sebastian F. and Koch, Federico and Schmiedel, Alexander and Holzapfel, Marco and Humeniuk, Alexander and R{\"o}hr, Merle I. S. and Mitric, Roland and Brixner, Tobias}, title = {Energy Transfer Between Squaraine Polymer Sections: From helix to zig-zag and All the Way Back}, series = {Journal of the American Chemical Society}, journal = {Journal of the American Chemical Society}, doi = {10.1021/jacs.5b03644}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-159607}, year = {2015}, abstract = {Joint experimental and theoretical study of the absorption spectra of squaraine polymers in solution provide evidence that two different conformations are present in solution: a helix and a zig-zag structure. This unique situation allows investigating ultrafast energy transfer processes between different structural segments within a single polymer chain in solution. The understanding of the underlying dynamics is of fundamental importance for the development of novel materials for light-harvesting and optoelectronic applications. We combine here femtosecond transient absorption spectroscopy with time-resolved 2D electronic spectroscopy showing that ultrafast energy transfer within the squaraine polymer chains proceeds from initially excited helix segments to zig-zag segments or vice versa, depending on the solvent as well as on the excitation wavenumber. These observations contrast other conjugated polymers such as MEH-PPV where much slower intrachain energy transfer was reported. The reason for the very fast energy transfer in squaraine polymers is most likely a close matching of the density of states between donor and acceptor polymer segments because of very small reorganization energy in these cyanine-like chromophores.}, language = {en} } @article{MuellerLuettigMalyetal.2019, author = {Mueller, Stefan and L{\"u}ttig, Julian and Mal{\´y}, Pavel and Ji, Lei and Han, Jie and Moos, Michael and Marder, Todd B. and Bunz, Uwe H. F. and Dreuw, Andreas and Lambert, Christoph and Brixner, Tobias}, title = {Rapid multiple-quantum three-dimensional fluorescence spectroscopy disentangles quantum pathways}, series = {Nature Communications}, volume = {10}, journal = {Nature Communications}, doi = {10.1038/s41467-019-12602-x}, url = {http://nbn-resolving.de/urn:nbn:de:bvb:20-opus-202529}, pages = {4735}, year = {2019}, abstract = {Coherent two-dimensional spectroscopy is a powerful tool for probing ultrafast quantum dynamics in complex systems. Several variants offer different types of information but typically require distinct beam geometries. Here we introduce population-based three-dimensional (3D) electronic spectroscopy and demonstrate the extraction of all fourth- and multiple sixth-order nonlinear signal contributions by employing 125-fold (1⨯5⨯5⨯5) phase cycling of a four-pulse sequence. Utilizing fluorescence detection and shot-to-shot pulse shaping in single-beam geometry, we obtain various 3D spectra of the dianion of TIPS-tetraazapentacene, a fluorophore with limited stability at ambient conditions. From this, we recover previously unknown characteristics of its electronic two-photon state. Rephasing and nonrephasing sixth-order contributions are measured without additional phasing that hampered previous attempts using noncollinear geometries. We systematically resolve all nonlinear signals from the same dataset that can be acquired in 8 min. The approach is generalizable to other incoherent observables such as external photoelectrons, photocurrents, or photoions.}, language = {en} }