TY - JOUR AU - Mohammed, Omar F. AU - Banerji, Natalie AU - Lang, Bernhard AU - Nibbering, Erik T J AU - Vauthey, Eric TI - Photoinduced bimolecular electron transfer investigated by femtosecond time-resolved infrared spectroscopy PY - 2006 JF - Journal of Physical Chemistry A JA - J. Phys. Chem. A SN - 1089-5639 VL - 110 IS - 51 SP - 13676 EP - 13680 L1 - http://pubs.acs.org/cgi-bin/article.cgi/jpcafh/2006/110/i51/pdf/jp066079x.pdf L2 - http://pubs.acs.org/cgi-bin/abstract.cgi/jpcafh/2006/110/i51/html/jp066079x.html L3 - http://pubs.acs.org/cgi-bin/abstract.cgi/jpcafh/2006/110/i51/abs/jp066079x.html M3 - 10.1021/jp066079x UR - http://dx.doi.org/10.1021/jp066079x N2 - Ultrafast infrared transient absorption spectroscopy is used to study the photoinduced bimolecular electron transfer reaction between perylene in the first singlet excited state and 1,4-dicyanobenzene in acetonitrile and dichloromethane. Following vibrational marker modes on both donor and acceptor sides in real time provides direct insight into the structural dynamics during the reaction. A band narrowing on a time scale of a few tens of picoseconds observed on the antisymmetric CN stretching vibration of the dicyanobenzene radical anion indicates that a substantial part of the excess energy is channeled into vibrational modes of the product, despite the fact that the reaction is weakly exergonic. An additional narrowing of the same band on a time scale of several hundreds of picoseconds observed in acetonitrile only is interpreted as a signature of the dissociation of the geminate ion pairs into free ions. ID - 847 ER -