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Comment on “Pseudo-Jahn–Teller and TICT-models: a photophysical comparison ofmeta-andpara-DMABN derivatives” [Chem. Phys. Lett. 305 (1999) 8]:The PICT model for dual fluorescence of aminobenzonitriles

Authors
Journal
Chemical Physics Letters
0009-2614
Publisher
Elsevier
Publication Date
Volume
320
Identifiers
DOI: 10.1016/s0009-2614(00)00230-x

Abstract

Abstract Due to the larger admixture of charge transfer (CT) in the intramolecular charge transfer (ICT) state than in the locally excited (LE) state of dual fluorescent molecules such as 4-(dimethylamino)benzonitrile, the radiative rate constant k f′(ICT) is smaller than k f(LE), irrespective of the ICT molecular structure. The validity of the TICT or PICT model can therefore not be tested with these data. The absence of dual fluorescence for 4-(methylamino)benzonitrile, 3-(dimethylamino)benzonitrile and two dicyano- N, N-dimethylanilines, which cannot be explained by the TICT hypothesis, is caused by their large energy gap Δ E(S 1, S 2), which prevents the ICT state from becoming lower in energy than LE.

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