Scientific article
English

Theory of fluorescence spectrum dynamics and its application to determining the relaxation characteristics of the solvent and intramolecular vibrations

Published inJournal of Molecular Liquids, vol. 298, no. 112016
Publication date2020
Abstract

A general analytical expression for the transient fluorescence spectrum is derived. The formation of a wave packet in the excited state of a fluorophore is described, assuming that the pump pulse has a Gaussian timeprofile. The expression explicitly connects the relaxation characteristics of the medium with the spectral dynamics of a fluorophore. Fitting the expression to experimental spectral dynamics allows obtaining the solvent relaxation function. So far this approach was applicable for the analysis of experimental data when the pump pulse does not populate excited sublevels of intramolecular high-frequency vibrational modes. Here, the approach is generalized to include vibrational relaxation in the excited electronic state. In this case, fitting to the experimental spectral dynamics provides reliable information not only on the solvent relaxation, but also on the relaxation time constants of intramolecular high-frequency vibrational modes. This approach is applied to the excited state dynamics of coumarin 153 in multiple solvents, obtained from broadband fluorescence upconversion spectroscopy.

Keywords
  • Microscopic liquid dynamics
  • Broadband fluorescence upconversion spectroscopy
  • Time dependent Stokes shift
  • Vibrational relaxation
  • Wave packet dynamics
Research groups
Citation (ISO format)
FEDUNOV, Roman G. et al. Theory of fluorescence spectrum dynamics and its application to determining the relaxation characteristics of the solvent and intramolecular vibrations. In: Journal of Molecular Liquids, 2020, vol. 298, n° 112016. doi: 10.1016/j.molliq.2019.112016
Main files (1)
Article (Published version)
accessLevelRestricted
Identifiers
Journal ISSN0167-7322
350views
1downloads

Technical informations

Creation13/09/2020 14:03:00
First validation13/09/2020 14:03:00
Update time15/03/2023 23:33:28
Status update15/03/2023 23:33:27
Last indexation31/10/2024 20:37:51
All rights reserved by Archive ouverte UNIGE and the University of GenevaunigeBlack