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.
Highlights
Coherent two-dimensional spectroscopy is a powerful tool for probing ultrafast quantum dynamics in complex systems
The great versatility of multidimensional techniques results from their ability to distinguish between specific nonlinear signal contributions
Such an approach should offer direct comparability between different signal contributions that is beneficial for interpretation purposes, especially because nonlinear signals show a strong dependence on the employed excitation conditions that might not be identical throughout separate measurements
Summary
Coherent two-dimensional spectroscopy is a powerful tool for probing ultrafast quantum dynamics in complex systems. As further shown in Supplementary Note 5 and Supplementary Fig. 7 and discussed in a similar scenario[61], the filtering effect by the laser spectrum removes from the complete manifold a number of pathways that involve the transition between |e0〉 and |g1〉, in the nonrephasing 1Q–0Q–1Q contribution.
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
