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Asian Journal of Physics Vol 31, Nos 9 – 10 (2022) 927-937

Fluorescence-detected multidimensional electronic spectroscopy

Amitav Sahu,Vivek Nagendra Bhat, Sanjoy Patra and Vivek Tiwari
Solid State and Structural Chemistry Unit, Indian Institute of Science, Bangalore-560 012, India

Multidimensional electronic spectroscopy (MES) is a state-of-the-art spectroscopic tool which provides two-dimensional (2D) contour map snapshots of ultrafast quantum dynamics with high temporal and spectral resolution. However, limited sensitivity of interferometric detection in the presence of scatter and lack of spatial resolution limits our understanding of several open questions, such as morphology dependence of exciton dissociation and photocurrent efficiency in photovoltaic thin films, and pure decoherence lifetimes on excited state coherences in photosynthetic proteins without ensemble averaging. We report a home-built fluorescence-detected MES (fMES) spectrometer based on a visible white-light continuum which overcomes the sensitivity and spatial resolution limitations of conventional MES. Our spectrometer is integrated with a confocal microscope to provide spatial resolution limited by the microscope objective. As a demonstration of sensitivity enhancement, we report high signal-to-noise ratio 2D coherence maps (CMs) which isolate vibrational coherences on the excited and ground electronic states of a laser dye based on the phase of vibrational quantum beats, at optical densities ~10× lower than what is typical for conventional MES approaches. © Anita Publications. All rights reserved.
Keywords: Coherences, Solvation, Fluorescence, Wavepackets, Femtosecond

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