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Updated: Jul 11, 2025

High Resolution Phonon-assisted Quasi-resonance Fluorescence Spectroscopy
Published on: June 28, 2016
Vibrationally Resolved Absorption, Fluorescence, and Preresonance Raman Spectroscopy of Isolated Pyronin Y Cation at
Sreekanta Debnath1, Alexander Schäfer1, Shun Ito2
1Institute of Physical Chemistry II, Karlsruhe Institute of Technology, Fritz-Haber-Weg 2, 76131 Karlsruhe, Germany.
Abstract:
Exploring how charge-changing affects the photoluminescence of small organic dyes presents challenges. Here, helium tagging photodissociation (PD) action spectroscopy in the gas phase and dispersed laser-induced fluorescence (DF) spectroscopy in the solid Ne matrix are used to compare the intrinsic photophysical properties of pyronin Y cation [PY]+ and its one electron-reduced neutral radical [PY]• at 5 K. Whereas the cation shows efficient visible photoluminescence, no emission from the neutral, in line with theoretical predictions, was detected. B3LYP/aug-cc-pVDZ calculations based on the TD-DFT/FCHT method allow for unambiguous assignment of recorded vibrationally resolved absorption and emission spectra. Surprisingly, our experimental sensitivity was high enough to also observe electronic preresonance Raman (ePR-Raman) spectra of [PY]+, with a significant efficiency factor (EF). These characteristics of the [PY]•/[PY]+ pair suggest that appropriately functionalized derivatives may open new perspectives in the area of in vivo bioimagining microscopy and find applications in various sophisticated stimulated-Raman spectroscopies.
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