Time-dependent density functional theory (TDDFT) study of the excited charge-transfer state formation of a series of aromatic donor-acceptor systems.

Singlet excitation energy calculations for a series of acceptor para-substituted N,N-dimethyl-anilines that are dual (4-(N,N-dimethylamino)benzonitrile, 4DMAB-CN, 4-(N,N-dimethylamino)benzaldhyde, 4DMAB-CHO, 1-methyl-7-cyano-2,3,4,5-tetrahydro-1H-1-benzazepine, NMC7) and nondual (4-aminobenzonitrile, 4AB-CN, 3-(N,N-dimethylamino)benzonitrile, 3DMAB-CN, and 4-nitro(N,N-dimethyl) aniline, 4DMAB-NO(2)) fluorescent have been performed using time-dependent density functional theory (TDDFT). The B3LYP and MPW1PW91 functionals with a 6-311+G(2d,p) (Bg) basis set have been used to compute excitation energies. Ground-state geometries were optimized using density functional theory (DFT) with both B3LYP and MPW1PW91 functionals combined with a 6-31G(d) basis set. For most of the molecules presented in this study, potential energy surfaces have been computed according to the coordinates related to the three following mechanisms proposed in the literature: twisting, wagging, and planar intramolecular charge transfer (ICT). Comparison of the three models for the different molecules leads to the conclusion that only the twisting ICT model is able to explain the low frequency, strongly solvent-dependent energy band present in the fluorescence spectra. According to this model, the 4AB-CN molecule is calculated to be nondual fluorescent in agreement with the experimental spectra. The single band observed in the fluorescence spectra of TMAB-CN (4-(N,N-dimethylamino)-3,5-(dimethyl)benzonitrile) is due to a large stabilization of the charge-transfer excited state along the twisting coordinate. The nondual fluorescence of the 4DMAB-NO(2) molecule is explained by the same mechanism. In the case of 3DMAB-CN, the single observed emission, which is solvent-dependent, has been assigned to the lowest charge-transfer excited state. The dual fluorescence of 4DMAB-CN and 4DMAB-CHO is explained within the twisting ICT model by a double mechanism (already proposed by Serrano et al.: Serrano-Andrés, L.; Merchán, M.; Roos, B. J.; Lindh, R. J. Am. Chem. Soc. 1995, 117, 3189) that involves the presence of two low-lying states close enough in energy. The observation of dual fluorescence in NMC7, that has been one of the origins of the planar ICT model put forward by Zachariasse et al. (Zachariasse, K.; van der Haar, T.; Hebecker, A.; Leinhos, U.; Kühnle, W. Pure Appl. Chem. 1993, 65, 1745), could be fully understood by a double mechanism within the twisting ICT model. Within the set of investigated molecules, our calculations confirm that the twisting ICT model is the only mechanism acceptable to explain the dual and nondual fluorescence phenomenon. Our calculations are in complete agreement with experimental data.