Exciton dissociation at donor-acceptor polymer heterojunctions: quantum nonadiabatic dynamics and effective-mode analysis

Abstract

The quantum-dynamical mechanism of photoinduced subpicosecond exciton dissociation and the concomitant formation of a charge-separated state at a TFB:F8BT polymer heterojunction is elucidated. The analysis is based upon a two-state vibronic coupling Hamiltonian including an explicit 24-mode representation of a phonon bath comprising high-frequency (C$=$C stretch) and low-frequency (torsional) modes. The initial relaxation behavior is characterized by coherent oscillations, along with the decay through an extended nonadiabatic coupling region. This region is located in the vicinity of a conical intersection hypersurface. A central ingredient of the analysis is a novel effective mode representation, which highlights the role of the low-frequency modes in the nonadiabatic dynamics. Quantum dynamical simulations were carried out using the multiconfiguration time-dependent Hartree (MCTDH) method.

References in corpus (3)

• Exciton Regeneration at Polymeric Semiconductor Heterojunctions
• Time-convolutionless master equation for mesoscopic electron-phonon systems
• Exciton Dissociation Dynamics in Model Donor-Acceptor Polymer Heterojunctions: I. Energetics and Spectra

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