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Updated: Aug 29, 2025

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Quantum dynamical study of inter-chain exciton transport in a regioregular P3HT model system at finite temperature:
Manel Mondelo-Martell1, Dominik Brey1, Irene Burghardt1
1Institute for Physical and Theoretical Chemistry, Goethe University Frankfurt, Max-von-Laue-Str. 7, 60438 Frankfurt am Main, Germany.
Abstract:
We report on quantum dynamical simulations of inter-chain exciton transport in a model of regioregular poly(3-hexylthiophene), rr-P3HT, at finite temperature using the Multi-Layer Multi-Configuration Time-Dependent Hartree method for a system of up to 63 electronic states and 180 vibrational modes. A Frenkel Hamiltonian of HJ aggregate type is used along with a reduced H-aggregate representation; electron-phonon coupling includes local high-frequency modes as well as anharmonic intermolecular modes. The latter are operative in mediating inter-chain transport by a mechanism of transient localization type. Strikingly, this mechanism is found to be of quantum coherent character and involves non-adiabatic effects. Using periodic boundary conditions, a normal diffusion regime is identified from the exciton mean-squared displacement, apart from early-time transients. Diffusion coefficients are found to be of the order of 3 × 10-3 cm2/s, showing a non-linear increase with temperature.
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