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RESEARCH PRODUCT
Quantum Chemical Parametrization and Spectroscopic Characterization of the Frenkel Exciton Hamiltonian for a J-Aggregate Forming Perylene Bisimide Dye
Oliver KühnAndreas KöhnJan SchulzeD. Ambroseksubject
Molecular StructureAbsorption spectroscopyChemistryExcitonCharge densityTime-dependent density functional theoryImideschemistry.chemical_compoundQuantum TheoryDensity functional theoryPhysical and Theoretical ChemistryAtomic physicsRotational–vibrational couplingPeryleneJ-aggregatePeryleneFluorescent Dyesdescription
Quantum chemical and quantum dynamical calculations are performed for a bay-substituted perylene bisimide dye up to its hexameric aggregate. The aggregate structure is determined by employing the self-consistent charge density functional tight-binding (SCC-DFTB) approach including dispersion corrections. It is characterized by a stabilization via two chains of hydrogen bonds facilitated by amide functionalities. Focusing on the central embedded dimer, the Coulomb coupling for this J-aggregate is determined by means of the time-dependent density functional theory (TDDFT) to be -514 cm(-1). Exciton vibrational coupling is treated within the shifted oscillator model from which five strongly coupled modes per monomer are selected for inclusion into a minimal dynamic model. Performing wave packet propagations for a model employing up to 7 electronic states and 30 vibrational modes using the multiconfiguration time-dependent Hartree method, aggregate absorption spectra are obtained and compared to experiment.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2012-09-19 | The Journal of Physical Chemistry A |