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Superexchange-mediated electronic energy transfer in a model dyad
Carles Curutchet1, Florian A Feist, Bernard Van Averbeke
1Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6 Canada.
Physical Chemistry Chemical Physics : PCCP
|June 15, 2010
Summary
Excitation energy transfer in a bridged chromophore system was studied. Electronic excitation extended over the bridge, increasing interaction and explaining model failures, but solvent polarity did not enhance coupling.
Area of Science:
- Photochemistry
- Molecular Spectroscopy
- Quantum Chemistry
Background:
- Understanding excitation energy transfer (EET) is crucial for designing advanced molecular materials.
- Traditional models like Förster resonance energy transfer (FRET) may not fully capture complex systems with significant electronic delocalization.
Purpose of the Study:
- To investigate EET in a perylene monoimide (PMI) donor-terrylene diimide (TDI) acceptor system linked by a pentaphenylene (pPh) spacer.
- To elucidate the role of the spacer and solvent polarity on electronic interactions and energy migration rates.
Main Methods:
- Time-dependent density functional theory (TD-DFT) calculations.
- Polarizable continuum model (PCM) for solvent effects.
- Single molecule spectroscopic studies.
Main Results:
- Electronic excitation on the PMI donor delocalized over the pPh bridge, exhibiting partial charge transfer character.
- This delocalization led to a threefold increase in electronic interaction between PMI and TDI.
- The Förster model failed to accurately predict energy migration rates due to this enhanced interaction.
Conclusions:
- The extended electronic wavefunctions and partial charge transfer significantly influence EET dynamics.
- Contrary to expectations, increased solvent polarity did not enhance electronic coupling between the chromophores.
- Detailed analysis of excited-state wavefunctions is essential for understanding EET in such complex systems.
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