Rapid multiple-quantum three-dimensional fluorescence spectroscopy disentangles quantum pathways.
Stefan MuellerJulian LüttigPavel MalýLei JiJie HanMichael MoosTodd B MarderUwe H F BunzAndreas DreuwChristoph LambertTobias BrixnerPublished in: Nature communications (2019)
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.
Keyphrases
- single molecule
- energy transfer
- monte carlo
- molecular dynamics
- living cells
- high resolution
- loop mediated isothermal amplification
- blood pressure
- quantum dots
- air pollution
- density functional theory
- particulate matter
- copy number
- fluorescent probe
- diffusion weighted imaging
- healthcare
- magnetic resonance
- social media
- contrast enhanced
- health information
- mass spectrometry
- sensitive detection
- real time pcr