Vibrational wave packet induced oscillations in two-dimensional electronic spectra. II. Theory

Autor(en)

Tomas Mancal, Alexandra Nemeth, Franz Milota, Vladimir Lukes, Harald Kauffmann, Jaroslaw Sperling

Abstrakt

We present a theory of vibrational modulation of two-dimensional coherent Fourier transformed electronic spectra. Based on an expansion of the system's energy gap correlation function in terms of Huang-Rhys factors, we explain the time-dependent oscillatory behavior of the absorptive and dispersive parts of two-dimensional spectra of a two-level electronic system, weakly coupled to intramolecular vibrational modes. The theory predicts oscillations in the relative amplitudes of the rephasing and nonrephasing parts of the two-dimensional spectra, and enables to analyze time-dependent two-dimensional spectra in terms of simple elementary components whose line shapes are dictated by the interaction of the system with the solvent only. The theory is applicable to both low and high energy (with respect to solvent induced line broadening) vibrations. The results of this paper enable to qualitatively explain experimental observations on low energy vibrations presented in the preceding paper [A. Nemeth , J. Chem. Phys. 132, 184514 (2010)] and to predict the time evolution of two-dimensional spectra in ultrafast ultrabroadband experiments on systems with high energy vibrations.

Organisation(en)

Institut für Physikalische Chemie, Elektronische Materialeigenschaften

Externe Organisation(en)

Charles University Prague, Ludwig-Maximilians-Universität München, Slovak University of Technology in Bratislava, Newport Spectra-Physics Gmbh

Journal

Journal of Chemical Physics

Band

132

ISSN

0021-9606

DOI

https://doi.org/10.1063/1.3404405

Publikationsdatum

2010

Peer-reviewed

Ja

ÖFOS 2012

103015 Kondensierte Materie

Link zum Portal

https://ucrisportal.univie.ac.at/de/publications/b4245d2d-3faf-43c1-8d72-763c9dacb4f5