Abstract: Nuclear wavepacket dynamics of the excited states of azulene – the representative example of anti-Kasha emitters – has been investigated to gain an insight into its non-trivial emission behavior in solution. Wavepacket propagation following the S0 → S2 excitation leads to a decrease in the population of the S2 state to ca. 90 % in 20 ps. According to simulations with various sets of normal modes, only three in-plane modes of azulene (Q16, Q33 and Q39) with the largest vibronic couplings drive the S2 → S1 internal conversion due to the large S2-S1 energy gap, while the other modes are “frozen”. A comparison of the excited state dynamics of azulene and its 2-chloro-, 2-hydroxy- and 2-dimethylamino-substituted derivatives reveals that the non-radiative events in the early time (up to 20 ps), which are driven by the interplay of the electronic energy gap and vibronic couplings, establish the trend in the experimental photoluminescence efficiency of azulene-based molecules in solution.

Cite: Shekhovtsov N.A. , Bushuev M.B.
Excited state dynamics of azulene and its derivatives: The impact of energy gap and vibronic coupling on anti-Kasha emission in solution
Journal of Molecular Liquids. 2025. V.425. 127260 :1-10. DOI: 10.1016/j.molliq.2025.127260 OpenAlex

Dates:

Submitted:	Dec 25, 2024
Accepted:	Feb 26, 2025
Published online:	Mar 1, 2025
Published print:	May 1, 2025

Identifiers:

OpenAlex:

W4408080153

Citing: Пока нет цитирований

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