Abstract
Theoretical insight is provided into excited-state intramolecular proton transfer based on a time-dependent density-functional theory method for 4′-dimethylaminoflavonol in the highly polar solvent acetonitrile. The calculated absorption and fluorescence spectra are in good agreement with the experimental results. Calculated hydrogen-bond energies and infrared vibrational spectra point to a strengthening of hydrogen bonding in the excited state. A frontier molecular orbital analysis illustrates that the nature of the hydrogen-bond enhancement is charge redistribution upon photo-excitation, which has been quantitatively confirmed by Mulliken, Hirshfeld, and natural bond orbital charge analyses. A reduced density gradient function provides a visual confirmation of the observed phenomenon of hydrogen-bond strengthening. Thus, the 4′-dimethylaminoflavonol molecule in highly polar acetonitrile can adopt a twisted intramolecular charge-transfer state. According to our calculations, intramolecular hydrogen bonds can facilitate intramolecular proton transfer in the twisted intramolecular charge-transfer state. Potential energy curves show that excited-state intramolecular proton transfer can occur because of the relatively low potential energy barrier.
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