Ultrafast photo-induced charge transfer unveiled by two-dimensional electronic spectroscopy
- Author(s)
- Oliver Bixner, Vladimir Lukes, Tomas Mancal, Jürgen Hauer, Franz Milota, Michael Fischer, Igor Pugliesi, Maximilian Bradler, Walther Schmid, Eberhard Riedle, Harald Kauffmann, Niklas Christensson
- 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
- Organisation(s)
- Department of Organic Chemistry, Department of Physical Chemistry, Electronic Properties of Materials
- External organisation(s)
- Slovak University of Technology in Bratislava, Charles University Prague, Ludwig-Maximilians-Universität München
- Journal
- Journal of Chemical Physics
- Volume
- 136
- No. of pages
- 12
- ISSN
- 0021-9606
- DOI
- https://doi.org/10.1063/1.4720492
- Publication date
- 2012
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104017 Physical chemistry, 1030 Physics, Astronomy
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/ultrafast-photoinduced-charge-transfer-unveiled-by-twodimensional-electronic-spectroscopy(f1cb2e3e-cfab-46a3-8f8a-b3cb496795ed).html