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Main Authors: Jindal, Vishal, Milner, Scott T.
Format: Preprint
Published: 2025
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Online Access:https://arxiv.org/abs/2510.18677
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author Jindal, Vishal
Milner, Scott T.
author_facet Jindal, Vishal
Milner, Scott T.
contents Charge carriers in organic semiconductors form polarons, which are self-localized states stabilized by interactions with their environment. Using a dielectric-stabilized tight-binding model parameterized from first-principles calculations, we compute ground and excited polaron states in poly(3-hexylthiophene) (P3HT). Our results quantitatively reproduce key mid-infrared absorption features, notably the chain-length-dependent shift of the intrachain polaron excitation peak (peak B) and its variation between regioregular and regiorandom P3HT. Comparison to an alternative stabilization mechanism based on local ring distortions reveals that dielectric polarization dominates polaron formation, as ring distortions yield insufficient binding and excitation energies inconsistent with experiments. These findings clarify the microscopic origin of polarons in conjugated polymers and provide a predictive framework linking polaron energetics to spectroscopic observables, advancing the understanding of charge transport in organic semiconductors.
format Preprint
id arxiv_https___arxiv_org_abs_2510_18677
institution arXiv
publishDate 2025
record_format arxiv
spellingShingle Modeling Polaron Excitations and Stabilization Mechanisms in Conjugated Polymers
Jindal, Vishal
Milner, Scott T.
Materials Science
Charge carriers in organic semiconductors form polarons, which are self-localized states stabilized by interactions with their environment. Using a dielectric-stabilized tight-binding model parameterized from first-principles calculations, we compute ground and excited polaron states in poly(3-hexylthiophene) (P3HT). Our results quantitatively reproduce key mid-infrared absorption features, notably the chain-length-dependent shift of the intrachain polaron excitation peak (peak B) and its variation between regioregular and regiorandom P3HT. Comparison to an alternative stabilization mechanism based on local ring distortions reveals that dielectric polarization dominates polaron formation, as ring distortions yield insufficient binding and excitation energies inconsistent with experiments. These findings clarify the microscopic origin of polarons in conjugated polymers and provide a predictive framework linking polaron energetics to spectroscopic observables, advancing the understanding of charge transport in organic semiconductors.
title Modeling Polaron Excitations and Stabilization Mechanisms in Conjugated Polymers
topic Materials Science
url https://arxiv.org/abs/2510.18677