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M. Hoffmann, Z.G. Soos, and K. Leo
Absorption spectra and band structure of mixed Frenkel-charge-transfer vibronic states in one-dimensional molecular crystals,
Nonlinear Optics 29 (2002) 227-237.

 
Abstract
We discuss the excited state structure of a one-dimensional molecular crystal. As in the Holstein model, we consider one Frenkel exciton with nearest-neighbor hopping and linear coupling to one internal vibration. Additionally, we include charge-transfer (CT) excitons that couple to the same vibrational mode and mix with the Frenkel exciton. The excited states of this model Hamiltonian are investigated by numerical diagonalization. For this, we represent the Hamiltonian in a displaced oscillator (Lang-Firsov) basis and use a problem-adapted truncation scheme for the phonon basis. Thus, the complete optical spectrum becomes accessible for weak up to intermediate electronic coupling. As an example, we discuss the exciton structure of the quasi-one-dimensional molecular crystals of PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N-N'-dimethylperylene-3,4,9,10-dicarboximide). The experimental linear absorption spectra can be well described by the k=0 states using appropriate parameter sets. We present the resulting band structure and compare the k=pi states with emission spectra.
 
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last updated: M. Hoffmann, Dec 2007