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RESEARCH PRODUCT
Excited states of [3.3](4,4')biphenylophane: the role of charge-transfer excitations in dimers with pi-pi interaction.
Andreas KöhnMathias Pabstsubject
chemistry.chemical_compoundchemistryIntramolecular forceDimerExcited stateSinglet fissionStrong interactionUltrafast laser spectroscopySinglet statePhysical and Theoretical ChemistryAtomic physicsExcitationdescription
The singlet and triplet electronic excitation manifold of [3.3](4,4')biphenylophane (BPP), an intramolecular dimer, and 4,4'-dimethylbiphenyl (DMBP), the corresponding monomer, has been analyzed by employing the approximate coupled-cluster singles and doubles model (CC2). The calculated triplet-triplet and singlet-singlet transient absorption spectra show good agreement with recent experimental results. The calculations suggest a strong interaction of the two biphenyl moieties of BPP in the first singlet and triplet excited states due to the overlapping pi-electron systems, and Forster-Dexter theory for weak coupling cannot be applied. Both the first excited singlet and triplet states of BPP can be characterized as excimeric states with a strong admixture of charge-transfer contributions.
| year | journal | country | edition | language |
|---|---|---|---|---|
| 2010-01-09 | The journal of physical chemistry. A |