Vibrational wave packet induced oscillations in two-dimensional electronic spectra. II. Theory
- Author(s)
- Tomas Mancal, Alexandra Nemeth, Franz Milota, Vladimir Lukes, Harald Kauffmann, Jaroslaw Sperling
- Abstract
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(s)
- Department of Physical Chemistry, Electronic Properties of Materials
- External organisation(s)
- Charles University Prague, Ludwig-Maximilians-Universität München, Slovak University of Technology in Bratislava, Newport Spectra-Physics Gmbh
- Journal
- Journal of Chemical Physics
- Volume
- 132
- ISSN
- 0021-9606
- DOI
- https://doi.org/10.1063/1.3404405
- Publication date
- 2010
- Peer reviewed
- Yes
- Austrian Fields of Science 2012
- 103015 Condensed matter
- Portal url
- https://ucrisportal.univie.ac.at/en/publications/b4245d2d-3faf-43c1-8d72-763c9dacb4f5