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M. Hoffmann, K. Schmidt, T. Fritz, T. Hasche, V. M. Agranovich, K. Leo,
The lowest energy Frenkel and charge-transfer excitons in quasi-one-dimensional structures:
application to MePTCDI and PTCDA crystals
,
Chem. Phys. 258 (2000) 73-96.
 
Abstract
We consider the exciton states in quasi-one-dimensional organic crystals with strong orbital overlap between neighboring molecules. In such crystals, the energy difference between the lowest Frenkel exciton and the nearest-neighbor charge-transfer excitons becomes small and their strong mixing determines the nature of the lowest energy states. We discuss these effects for crystalline MePTCDI (N-N'-dimethylperylene-3,4,9,10-dicarboximide) and PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride). To model the exciton states we use a Hamiltonian which includes the mixing of Frenkel excitons with several vibronic levels and charge-transfer excitons. With appropriate fitting parameters, we demonstrate that this model can explain the main features of the low temperature absorption spectra. Polarized absorption spectra of MePTCDI show different polarization ratios for the various absorption peaks. This polarization behavior is discussed as a qualitative proof for the varying contribution of the charge-transfer excitons, which have a transition dipole direction different from that of the Frenkel excitons.
 
DOI:10.1016/S0301-0104(00)00157-9 (direct link to publisher)
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last updated: M. Hoffmann, Dec 2007