Shedding Light on Excited-State Structures by Theoretical Analysis of Femtosecond Transient Infrared Spectra: Intramolecular Charge Transfer in 4-(Dimethylamino)benzonitrile
作者： Jens Dreyer , Andreas Kummrow
DOI: 10.1021/JA992095E
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摘要: We performed a detailed theoretical analysis of femtosecond transient infrared spectra to determine excited-state structures involved in photoinduced intramolecular charge transfer (ICT) 4-(dimethylamino)benzonitrile (DMABN). For comparison, 4-aminobenzonitrile (ABN) is studied. present the first ab initio CASSCF study with all states under consideration being fully optimized. derive two different models for locally excited (LE) states: planar and novel pyramidal conformation. Three mechanisms are treated ICT state formation: twisted (TICT), pseudo-Jahn−Teller (PICT), rehybridized (RICT) models. By use this combined experimental approach, we can evaluate respective thus provide new insight into process. assign LE ABN, and, contrast, DMABN. conclusively rule out RICT as mechanism Although our results favor TICT mechani...
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