Time‐dependent density functional theory study on hydrogen‐bonded intramolecular charge‐transfer excited state of 4‐dimethylamino‐benzonitrile in methanol

The time‐dependent density functional theory (TDDFT) method was carried out to investigate the hydrogen‐bonded intramolecular charge‐transfer (ICT) excited state of 4‐dimethylaminobenzonitrile (DMABN) in methanol (MeOH) solvent. We demonstrated that the intermolecular hydrogen bond C≡N···HO formed between DMABN and MeOH can induce the C≡N stretching mode shift to the blue in both the ground state and the twisted intramolecular charge‐transfer (TICT) state of DMABN. Therefore, the two components at 2091 and 2109 cm−1 observed in the time‐resolved infrared (TRIR) absorption spectra of DMABN in MeOH solvent were reassigned in this work. The hydrogen‐bonded TICT state should correspond to the blue‐side component at 2109 cm−1, whereas not the red‐side component at 2091 cm−1 designated in the previous study. It was also demonstrated that the intermolecular hydrogen bond C≡N···HO is significantly strengthened in the TICT state. The intermolecular hydrogen bond strengthening in the TICT state can facilitate the deactivation of the excited state via internal conversion (IC), and thus account for the fluorescence quenching of DMABN in protic solvents. Furthermore, the dynamic equilibrium of these electronically excited states is explained by the hydrogen bond strengthening in the TICT state. © 2008 Wiley Periodicals, Inc. J Comput Chem, 2008

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