Photoinduced bimolecular electron transfer investigated by femtosecond time-resolved infrared spectroscopy

Omar Abdelsaboor, Natalie Banerji, Bernhard Lang, Erik T.J. Nibbering*, Eric Vauthey

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

31 Scopus citations

Abstract

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.

Original languageEnglish (US)
Pages (from-to)13676-13680
Number of pages5
JournalJournal of Physical Chemistry A
Volume110
Issue number51
DOIs
StatePublished - Dec 28 2006

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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