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

Hiroyuki Tamura; Eric R. Bittner; Irene Burghardt

doi:10.1063/1.2431358

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

Hiroyuki Tamura, Eric R. Bittner, Irene Burghardt

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56 Citations (Scopus)

Abstract

The quantum-dynamical mechanism of photoinduced subpicosecond exciton dissociation and the concomitant formation of a charge-separated state at a semiconducting 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 (CC 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 method.

Original language	English
Article number	021103
Journal	Journal of Chemical Physics
Volume	126
Issue number	2
DOIs	https://doi.org/10.1063/1.2431358
Publication status	Published - 2007

ASJC Scopus subject areas

Physics and Astronomy(all)
Physical and Theoretical Chemistry

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title = "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 semiconducting 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 (CC 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 method.",

author = "Hiroyuki Tamura and Bittner, {Eric R.} and Irene Burghardt",

note = "Funding Information: We would like to thank Andrey Pereverzev, Etienne Gindensperger, and Lorenz Cederbaum for constructive discussions. This work was supported by the ANR-05-NANO-051-02 and ANR-NT05-3-42315 projects, by NSF grant CHE-0345324, and by the Robert Welch Foundation. ",

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T2 - Quantum nonadiabatic dynamics and effective-mode analysis

AU - Tamura, Hiroyuki

AU - Bittner, Eric R.

AU - Burghardt, Irene

N1 - Funding Information: We would like to thank Andrey Pereverzev, Etienne Gindensperger, and Lorenz Cederbaum for constructive discussions. This work was supported by the ANR-05-NANO-051-02 and ANR-NT05-3-42315 projects, by NSF grant CHE-0345324, and by the Robert Welch Foundation.

PY - 2007

Y1 - 2007

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AB - The quantum-dynamical mechanism of photoinduced subpicosecond exciton dissociation and the concomitant formation of a charge-separated state at a semiconducting 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 (CC 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 method.

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