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Density of states and wave function localization in disordered conjugated polymers: a large scale computational
Nenad Vukmirović1, Lin-Wang Wang
1Materials Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA.
Electronic structure calculations reveal that electrostatic potential fluctuations, not conjugation breaks, localize hole states in disordered conjugated polymers. This finding is modeled by a tight-binding approach with Gaussian on-site energy distributions.
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Area of Science:
- Materials Science
- Computational Chemistry
- Condensed Matter Physics
Background:
- Disordered conjugated polymers are crucial for organic electronics.
- Understanding their electronic structure is key to device performance.
- Previous models often oversimplified disorder effects.
Purpose of the Study:
- To investigate the electronic structure of strongly disordered conjugated polymers.
- To identify the primary cause of charge carrier localization.
- To develop a more accurate theoretical model for these materials.
Main Methods:
- Large-scale electronic structure calculations.
- Density functional theory (DFT) based charge patching method for Hamiltonian construction.
- Overlapping fragments method for efficient Hamiltonian diagonalization.
Main Results:
- Hole states are localized by electrostatic potential fluctuations, not conjugation breaks.
- The density of hole states exhibits an exponential decay tail.
- A 1D tight-binding model with correlated Gaussian on-site energies captures key features.
Conclusions:
- Electrostatic disorder is the dominant factor in hole state localization.
- The developed model provides a robust framework for predicting electronic properties.
- This work advances the understanding of charge transport in organic semiconductors.