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Double-quantum two-dimensional electronic spectroscopy of a three-level system: Experiments and simulations
Alexandra Nemeth1, Franz Milota, Tomás Mancal
1Electronic Properties of Materials, Faculty of Physics, University of Vienna, Strudlhofgasse 4, Vienna 1090, Austria. alexandra.nemeth@univie.ac.at
The Journal of Chemical Physics
|September 14, 2010
Summary
Double-quantum coherence two-dimensional electronic spectroscopy reveals correlated spectral fluctuations in excited electronic states of solvated molecules. This advanced technique provides insights into system-bath interactions and electronic state dynamics.
Area of Science:
- Physical Chemistry
- Spectroscopy
- Quantum Dynamics
Background:
- Understanding dynamic fluctuations of electronic states in solvated molecules is crucial for characterizing molecular behavior.
- Two-dimensional electronic spectroscopy (2D ES) offers powerful insights into ultrafast dynamics.
Purpose of the Study:
- To probe dynamic fluctuations of electronic states using double-quantum coherence two-dimensional (2Q2D) electronic spectroscopy.
- To investigate the correlation of spectral fluctuations between different electronically excited states.
Main Methods:
- Utilized double-quantum coherence two-dimensional (2Q2D) and single-quantum two-dimensional (1Q2D) electronic spectroscopy.
- Employed 23 fs pulses centered at the linear absorption maximum for experiments on solvated Rhodamine 6G.
- Applied a three-level model with second-order cumulant expansion to analyze the third-order response function.
Main Results:
- The 2Q2D spectrum showed three peaks with alternating signs, and the 1Q2D spectrum exhibited a negative peak from excited state absorption.
- Analysis revealed that a simple homogeneous limit model could not explain the observed spectral features.
- The three-level model provided good agreement with both 1Q2D and 2Q2D experimental data.
Conclusions:
- Spectral fluctuations in the probed electronic states are highly correlated, indicating modulation by a common nuclear bath.
- The findings highlight the utility of 2Q2D electronic spectroscopy for studying coupled electronic state dynamics.
- The study demonstrates similarities in the nature of electronic transitions influencing correlated fluctuations.
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