System-Dependent Signatures of Electronic and Vibrational Coherences in Electronic Two-Dimensional Spectra
- Author(s)
- Tomas Mancal, Niklas Christensson, Vladimir Lukes, Franz Milota, Oliver Bixner, Harald Kauffmann, Jürgen Hauer
- Abstract
In this work, we examine vibrational coherence in a molecular monomer, where time evolution of a nuclear wavepacket gives rise to oscillating diagonal- and off-diagonal peaks in two-dimensional electronic spectra. We find that the peaks oscillate out-of-phase, resulting in a cancellation in the corresponding pump probe spectra. Our results confirm the unique disposition of two-dimensional electronic spectroscopy (2D-ES) for the study of coherences. The oscillation pattern is in excellent agreement with the diagrammatic analysis of the third-order nonlinear response. We show how 2D-ES can be used to distinguish between ground- and excited-state wavepackets. On the basis of our results, we discuss coherences in coupled molecular aggregates involving both electronic and nuclear degrees of freedom. We conclude that a general distinguishing criterion based on the experimental data alone cannot be devised.
- Organisation(s)
- Electronic Properties of Materials, Department of Organic Chemistry, Department of Physical Chemistry
- External organisation(s)
- Charles University Prague, Slovak University of Technology in Bratislava
- Journal
- The Journal of Physical Chemistry Letters
- Volume
- 3
- Pages
- 1497-1502
- No. of pages
- 6
- DOI
- https://doi.org/10.1021/jz300362k
- Publication date
- 2012
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 104017 Physical chemistry, 103018 Materials physics
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/systemdependent-signatures-of-electronic-and-vibrational-coherences-in-electronic-twodimensional-spectra(05c36ba6-82b1-44a7-9abd-8d6f4a9fb62d).html