Journal of Physical Chemistry A, Vol.107, No.40, 8327-8329, 2003
Intramolecular reorganization of the electron donor N,N-dimethylaniline
Intramolecular reorganization is investigated for the transition DMA --> DMA(+) of the electron donor N,N-dimethylaniline. Optimized geometries and normal modes are calculated quantum chemically for DMA and DMAI. Partial reorganization energies of the normal modes are determined. Several modes between 100 and 1700 cm(-1) are found to couple to the transition. The Franck-Condon weighted density of states is evaluated, which enters the nonadiabatic rate expression. It is found that the intramolecular modes can be effective as energy acceptors over a wide range of excess energies.