Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy

Oliver Bixner, Vladimír Lukeš, Tomá Mančal, Jürgen Hauer, Franz Milota, Michael Fischer, Igor Pugliesi, Maximilian Bradler, Walther Schmid, Eberhard Riedle, Harald F. Kauffmann, Niklas Christensson

Research output: Contribution to journalArticlepeer-review

53 Scopus citations

Abstract

The interaction of exciton and charge transfer (CT) states plays a central role in photo-induced CT processes in chemistry, biology, and physics. In this work, we use a combination of two-dimensional electronic spectroscopy (2D-ES), pump-probe measurements, and quantum chemistry to investigate the ultrafast CT dynamics in a lutetium bisphthalocyanine dimer in different oxidation states. It is found that in the anionic form, the combination of strong CT-exciton interaction and electronic asymmetry induced by a counter-ion enables CT between the two macrocycles of the complex on a 30 fs timescale. Following optical excitation, a chain of electron and hole transfer steps gives rise to characteristic cross-peak dynamics in the electronic 2D spectra, and we monitor how the excited state charge density ultimately localizes on the macrocycle closest to the counter-ion within 100 fs. A comparison with the dynamics in the radical species further elucidates how CT states modulate the electronic structure and tune fs-reaction dynamics. Our experiments demonstrate the unique capability of 2D-ES in combination with other methods to decipher ultrafast CT dynamics.

Original languageEnglish
Article number204503
JournalJournal of Chemical Physics
Volume136
Issue number20
DOIs
StatePublished - 28 May 2012
Externally publishedYes

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