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A TDDFT Study on the Excited-State Intramolecular Proton Transfer (ESIPT): Excited-State Equilibrium Induced by Electron Density Swing

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Abstract

One important issue of current interest is the excited-state equilibrium for some ESITP dyes. However, so far, the information about the driving forces for excited-state equilibrium is very limited. In this work, the time-dependent density functional theory (TDDFT) method was employed to investigate the nature of the excited-state intramolecular proton transfer (ESIPT). The geometric structures, vibrational frequencies, frontier molecular orbitals (MOs) and the potential-energy curves for 1-hydroxy-11H-benzo[b]fluoren-11-one (HHBF) in the ground and the first singlet excited state were calculated. Analysis of the results shows that the intramolecular hydrogen bond of HHBF is strengthened from E to E*. Moreover, it is found that electron density swing between the proton acceptor and donor provides the driving forces for the forward and backward ESIPT, enabling the excited-state equilibrium to be established. Furthermore, we proposed that the photoexcitation and the interchange of position for electron-donating and electron-withdrawing groups are the main reasons for the electron density swing. The potential-energy curves suggest that the forward ESIPT and backward ESIPT may happen on the similar timescale, which is faster than the fluorescence decay of both E* and K* forms.

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Authors and Affiliations

  1. State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, 116023, China

    Mingzhen Zhang, Dapeng Yang, Baiping Ren & Dandan Wang

  2. Physics Laboratory, North China University of Water Resources and Electric Power, 36 Beihuan Road, Zhengzhou, 450011, China

    Mingzhen Zhang, Dapeng Yang, Baiping Ren & Dandan Wang

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  1. Mingzhen Zhang
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  2. Dapeng Yang
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  3. Baiping Ren
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  4. Dandan Wang
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Correspondence to Dapeng Yang.

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Zhang, M., Yang, D., Ren, B. et al. A TDDFT Study on the Excited-State Intramolecular Proton Transfer (ESIPT): Excited-State Equilibrium Induced by Electron Density Swing. J Fluoresc 23, 761–766 (2013). https://doi.org/10.1007/s10895-013-1195-9

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  • DOI: https://doi.org/10.1007/s10895-013-1195-9

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