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Intermediate Polaronic Charge Transport in Organic Crystals from First Principles

Chang, Benjamin K. and Zhou, Jin-Jian and Lee, Nien-En and Bernardi, Marco (2021) Intermediate Polaronic Charge Transport in Organic Crystals from First Principles. . (Unpublished)

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Predicting the electrical properties of organic molecular crystals (OMCs) is challenging due to their complex crystal structures and electron-phonon (e-ph) interactions. Charge transport in OMCs is conventionally categorized into two limiting regimes − band transport, characterized by weak e-ph interactions and governed by low-energy intermolecular vibrations, and charge hopping, where strong e-ph interactions form localized polarons that diffuse slowly via thermally activated processes. However, between these two limiting cases there is a common, but less well understood intermediate transport regime where polarons are present but transport does not occur via hopping. Here we show accurate first-principles calculations of the carrier mobility in the intermediate charge transport regime, and shed light on its microscopic origin. We combine a finite-temperature cumulant method to describe the strong e-ph interactions and Green-Kubo transport calculations. Our study on naphthalene crystal demonstrates that we can accurately predict the electron mobility in the intermediate regime, within a factor of 1.5−2 of experiment between 100−300 K. Our analysis reveals that electrons couple strongly with both inter- and intramolecular phonons in the intermediate regime, as evidenced by the formation of a broad polaron satellite peak in the electron spectral function and by significant changes in the quasiparticle peak linewidth and spectral weight. These higher-order e-ph interactions make transport calculations based on the Boltzmann equation inadequate to describe the intermediate regime. Our study advances the understanding of the intermediate regime and paves the way for quantitative modeling of charge transport in complex organic crystals.

Item Type:Report or Paper (Discussion Paper)
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URLURL TypeDescription Paper
Zhou, Jin-Jian0000-0002-1182-9186
Bernardi, Marco0000-0001-7289-9666
Additional Information:This work was supported by the National Science Foundation under Grant No. DMR-1750613. J.-J.Z. acknowledges support from the Joint Center for Artificial Photosynthesis, a DOE Energy Innovation Hub, as follows: The development of some computational methods employed in this work was supported through the Office of Science of the US Department of Energy under Award No. DE-SC0004993. N.-E. Lee was supported by the Air Force Office of Scientific Research through the Young Investigator Program, Grant FA9550-18-1-0280. This research used resources of the National Energy Research Scientific Computing Center (NERSC), a U.S. Department of Energy Office of Science User Facility located at Lawrence Berkeley National Laboratory, operated under Contract No. DE-AC02-05CH11231.
Funding AgencyGrant Number
Department of Energy (DOE)DE-SC0004993
Air Force Office of Scientific Research (AFOSR)FA9550-18-1-0280
Department of Energy (DOE)DE-AC02-05CH11231
Record Number:CaltechAUTHORS:20210716-222534684
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:109890
Deposited By: George Porter
Deposited On:16 Jul 2021 22:56
Last Modified:16 Jul 2021 22:56

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