System-Dependent Signatures of Electronic and Vibrational Coherences in Electronic Two-Dimensional Spectra

Autor(en)

Tomas Mancal, Niklas Christensson, Vladimir Lukes, Franz Milota, Oliver Bixner, Harald Kauffmann, Jürgen Hauer

Abstrakt

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(en)

Elektronische Materialeigenschaften, Institut für Organische Chemie, Institut für Physikalische Chemie

Externe Organisation(en)

Charles University Prague, Slovak University of Technology in Bratislava

Journal

The Journal of Physical Chemistry Letters

Band

3

Seiten

1497-1502

Anzahl der Seiten

6

DOI

https://doi.org/10.1021/jz300362k

Publikationsdatum

2012

Peer-reviewed

Ja

ÖFOS 2012

104017 Physikalische Chemie, 103018 Materialphysik

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/05c36ba6-82b1-44a7-9abd-8d6f4a9fb62d