Predicting fluorescence quantum yields for molecules in solution: A critical assessment of the harmonic approximation and the choice of the lineshape function
Entity
UAM. Departamento de QuímicaPublisher
AIP PublishingDate
2020-02-05Citation
The Journal of Chemical Physics 152.5 (2020): 054107ISSN
0021-9606Funded by
R.M. and A.H. acknowledge financial support within the ERC Consolidator Grant “DYNAMO” (Grant No. 646737). R.M. and J.H. thank the Deutsche Forschungsgemeinschaft for support of this work within the Research Group FOR 1809. This research was partially supported by the project STIM–REI, Contract Number: KK.01.1.1.01.0003, funded by the European Union through the European Regional Development Fund—the Operational Programme Competitiveness and Cohesion 2014-2020 (KK.01.1.1.01). V.B.K. and M.B. acknowledge computational facilities of the supercomputer SRCE at the University of Zagreb as well as doctoral study of Biophysics at the University of SplitProject
info:eu-repo/grant/Agreement/EC/ERC-COG/646737Editor's Version
https://doi.org/10.1063/1.5143212Subjects
QuímicaNote
The following article appeared in The Journal of Chemical Physics 152.5 (2020): 054107 and may be found at https://doi.org/10.1063/1.5143212Rights
© AIPAbstract
For the rational design of new fluorophores, reliable predictions of fluorescence quantum yields from first principles would be of great help.
However, efficient computational approaches for predicting transition rates usually assume that the vibrational structure is harmonic. While
the harmonic approximation has been used successfully to predict vibrationally resolved spectra and radiative rates, its reliability for nonradiative rates is much more questionable. Since non-adiabatic transitions convert large amounts of electronic energy into vibrational energy,
the highly excited final vibrational states deviate greatly from harmonic oscillator eigenfunctions. We employ a time-dependent formalism
to compute radiative and non-radiative rates for transitions and study the dependence on model parameters. For several coumarin dyes,
we compare different adiabatic and vertical harmonic models (AS, ASF, AH, VG, VGF, and VH), in order to dissect the importance of
displacements, frequency changes, and Duschinsky rotations. In addition, we analyze the effect of different broadening functions (Gaussian,
Lorentzian, or Voigt). Moreover, to assess the qualitative influence of anharmonicity on the internal conversion rate, we develop a simplified
anharmonic model. We address the reliability of these models considering the potential errors introduced by the harmonic approximation
and the phenomenological width of the broadening function
Files in this item
Google Scholar:Humeniuk, Alexander
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Bužančić, Margarita
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Hoche, Joscha
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Cerezo Bastida, Javier
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Mitric, Roland
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Santoro, Fabrizio
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Koutecký, Vlasta Bonacic
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