A novel fluorescence molecule (2‑hydroxy‑4‑methoxyphenyl)(phenyl)‑methanone azine (HMPM) has been explored theoretically in this present work. Based on density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods, we investigate the excited state hydrogen bonding behaviors and excite state intramolecular proton transfer (ESIPT) process for HMPM molecule. Via simulating the reduced density gradient (RDG) versus sign(λ2)ρ, we firstly verify the double intramolecular hydrogen bonds (O1H2⋯N3 and O4H5⋯N6) for HMPM system. Comparing with the changes about these two hydrogen bonds (i.e., bond distances, bond angles and infrared (IR) vibrational spectra), we find that they should be enhanced in the first excited state upon the photo-excitation. The shortened hydrogen bonding distance of H2⋯N3 and H5⋯N6 provide the possibility for ESIPT reaction. Given the photo-excitation process, we confirm the charge redistribution around the hydrogen bonding moieties plays an important role as a driving force for the ESIPT process. Further, via constructing S0-state and S1-state potential energy surfaces (PESs), we confirm the excited state double proton transfer (ESDPT) is excludable since the high optimized energy and high potential energy barrier. While the low potential barrier for excited state single proton transfer path results in the ultrafast ESIPT reaction, which explains why the initial HMPM fluorescence peak cannot be detected in previous experimental phenomenon. This work not only clarifies the excited state dynamical behavior for HMPM system, but also explains previous experimental phenomenon and attributions about steady state spectra. We hope this work can facilitate novel applications based on the novel HMPM system in future.
Keywords: Charge density difference; Dual intramolecular hydrogen bonds; Frontier molecular orbital; Infrared vibrational spectra; Potential energy surface; Steady state spectra.
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