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Excited state dynamics of protonated keto uracil: intersystem crossing pathways in competition

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Abstract

The relaxation dynamics of protonated keto uracil has been investigated through cryogenic UV photodissociation spectroscopy. Steady-state spectroscopy and time-resolved photochemistry, including pump-probe photodissociation and kinetics of appearance of photofragments, are monitored over 10 orders of magnitude as a function of excess energy imparted in the bright \(^{\mathrm {1}}\uppi \uppi \)* state. Although photofragments are produced in the ground electronic state after internal conversion, the non-radiative decay mechanism abruptly changes with a slight increase of excess energy in the \(^{\mathrm {1}}\uppi \uppi \)* state. At the band origin, a three-step decay involving electronic couplings to the charge transfer \(^{\mathrm {1}}\hbox {n}_{\text {o}}\uppi \)* state and the triplet \(^{\mathrm {3}}\uppi \uppi \)* state with lifetimes in the range of \(10\,{\upmu }\hbox {s}\) and 2 ms, respectively, is proposed. However, the pathway through the charge transfer state closes a few hundreds of wavenumbers above the band origin. From this excess energy, the excited state population is transferred through a low energy barrier towards a region of the \(^{\mathrm {1}}\uppi \uppi \)* potential energy surface where a triple crossing with the \(^{\mathrm {3}}\uppi \uppi \)* state and the ground state is located. The experimental results are assigned with the help of ab initio calculations at the spin-component scaled coupled-cluster level.

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Data Availibility Statement

This manuscript has no associated data or the data will not be deposited. [Authors’ comment: The datasets generated during and/or analysed during the current study are available from the corresponding author on reasonable request.]

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Acknowledgements

We acknowledge the use of the computing facility MésoLUM of the LUMAT federation (FRLUMAT 2764) and MAGI of the University Paris 13.

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Authors and Affiliations

  1. Université Paris-Saclay, CNRS, Institut des Sciences Moléculaires d’Orsay, 91405, Orsay, France

    Jordan Dezalay, Michel Broquier, Satchin Soorkia & Gilles Grégoire

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  1. Jordan Dezalay
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  2. Michel Broquier
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  3. Satchin Soorkia
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  4. Gilles Grégoire
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Contributions

All authors conducted experiments, performed data analysis. GG performed calculations and wrote the manuscript.

Corresponding author

Correspondence to Gilles Grégoire.

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Dezalay, J., Broquier, M., Soorkia, S. et al. Excited state dynamics of protonated keto uracil: intersystem crossing pathways in competition. Eur. Phys. J. D 75, 17 (2021). https://doi.org/10.1140/epjd/s10053-020-00017-z

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