Journal of Physical Chemistry A, Vol.103, No.16, 3013-3019, 1999
Nonexponentialities in the ultrafast electron-transfer dynamics in the system oxazine 1 in N,N-dimethylaniline
Transient absorption experiments with probing in the blue part of the spectrum (440-500 nm) are performed for the electron-transfer system oxazine 1 in N,N-dimethylaniline. The experiments with high time resolution of better than 20 fs show pronounced modulations due to high-frequency wave packet motion (600 cm(-1)) in the excited electronic state of the oxazine I molecule before electron transfer. Additionally, modulations due to wave packet motion in the product state of oxazine 1 after complete charge separation are observed. The absorption transients related to the electron transfer from N,N-dimethylaniline to oxazine 1 are clearly nonmonoexponential with time constants of 30 and 80 fs. This behavior points to a strong adiabaticity of the electron-transfer reaction with a high relevance of nuclear motions.
Keywords:PUMP-PROBE SPECTROSCOPY;PHOTOSYNTHETIC REACTION CENTERS;VIBRATIONAL COHERENCE;RHODOBACTER-SPHAEROIDES;ABSORPTION-SPECTROSCOPY;WAVE-PACKET;FEMTOSECOND;FLUORESCENCE;OSCILLATIONS;MOLECULES