Time-dependent density functional theory study on the electronic excited-state hydrogen-bonding dynamics of 4-aminophthalimide (4AP) in aqueous solution: 4AP and 4AP–(H2O)1,2 clusters

Authors

  • Rui Wang,

    1. State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
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  • Ce Hao,

    Corresponding author
    1. State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
    • State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
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  • Peng Li,

    Corresponding author
    1. Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
    • Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China
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  • Ning-Ning Wei,

    1. State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
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  • Jingwen Chen,

    1. State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
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  • Jieshan Qiu

    1. State Key Laboratory of Fine Chemicals, School of Environmental and Biological Science and Technology, Dalian University of Technology, Dalian 116024, China
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Abstract

The time-dependent density functional theory (TDDFT) method has been carried out to investigate the excited-state hydrogen-bonding dynamics of 4-aminophthalimide (4AP) in hydrogen-donating water solvent. The infrared spectra of the hydrogen-bonded solute−solvent complexes in electronically excited state have been calculated using the TDDFT method. We have demonstrated that the intermolecular hydrogen bond C[DOUBLE BOND] O···H[BOND]O and N[BOND]H···O[BOND]H in the hydrogen-bonded 4AP−(H2O)2 trimer are significantly strengthened in the electronically excited state by theoretically monitoring the changes of the bond lengths of hydrogen bonds and hydrogen-bonding groups in different electronic states. The hydrogen bonds strengthening in the electronically excited state are confirmed because the calculated stretching vibrational modes of the hydrogen bonding C[DOUBLE BOND]O, amino N[BOND]H, and H[BOND]O groups are markedly red-shifted upon photoexcitation. The calculated results are consistent with the mechanism of the hydrogen bond strengthening in the electronically excited state, while contrast with mechanism of hydrogen bond cleavage. Furthermore, we believe that the transient hydrogen bond strengthening behavior in electroniclly excited state of chromophores in hydrogen-donating solvents exists in many other systems in solution. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010

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