Hannover 2016 – scientific programme
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MO: Fachverband Molekülphysik
MO 7: Femtosecond Spectroscopy 2
MO 7.4: Talk
Tuesday, March 1, 2016, 12:00–12:15, f102
Two-Dimensional Electronic Spectroscopy Can Fully Characterize the Population Transfer in Molecular Systems — •Jakub Dostál1, Barbora Benešová2, and Tobias Brixner1 — 1Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Am Hubland, 97074 Würzburg — 2Department of Mathematics, University of Würzburg, Emil-Fischer-Straße 40, 97074 Würzburg
Excitation energy transfer (EET) in complex systems often proceeds through series of intermediate states. One of the goals of time-resolved spectroscopy is to identify the spectral signatures of all of them in the acquired experimental data and to characterize the energy transfer scheme between them. It is well known that in the case of transient absorption (TA) spectra such a decomposition can be ambiguous even if many simplifying considerations (such as described below) are taken. The systematic decomposition of coherent 2D spectra has not been investigated to date.
Here we show that the unique retrieval of the complete set of rate constants and TA spectra of all states is possible by simultaneously fitting the 2D spectrum and absorption spectrum. An efficient implementation of the fitting routine is proposed. We focus on the ideal case of a system with well separated spectral bands, with no dark states present and with EET strictly governed by a set of linear rate equations of the first order. We also assume that the spectra of the intermediate states are not linearly dependent. This represents a theoretical basis for quantitative analysis of EET in experimental 2D spectra.