TY - JOUR
T1 - Structural Correlations and Percolation in Twisted Perylene Diimides Using a Simple Anisotropic Coarse-Grained Model
AU - Bowen, Alec S.
AU - Jackson, Nicholas E.
AU - Reid, Daniel R.
AU - De Pablo, Juan J.
N1 - Funding Information:
This work is supported by the Department of Energy, Office of Science, Basic Energy Sciences, Division of Materials Research Science and Engineering. N.E.J. thanks the Maria Goeppert Mayer Named Fellowship from Argonne National Laboratory for support. LAMMPS74 was used for atomistic simulations, and Visual Molecular Dynamics75 was used for visualization.
Publisher Copyright:
© 2018 American Chemical Society.
Copyright:
Copyright 2019 Elsevier B.V., All rights reserved.
PY - 2018/12/11
Y1 - 2018/12/11
N2 - Large, twisted, and fused conjugated molecular architectures have begun to appear more prominently in the organic semiconductor literature. From a modeling perspective, such structures present a challenge to conventional simulation techniques; atomistic resolutions are computationally inefficient, while traditional isotropic coarse-grained models do not capture the inherent anisotropies of the molecules. In this work, we develop a simple coarse-grained model that explicitly incorporates the anisotropy of these molecular architectures, thereby providing a route toward analyzing π-stacking, and thus qualitative electronic structure, at a computationally efficient coarse-grained resolution. Our simple coarse-grained model maintains relative orientations of conjugated rings, as well as inter-ring dihedrals, that are critical for understanding electronic and excitonic transport in bulk systems. We apply this model to understand structural correlations in several recently synthesized perylene diimide (PDI)-based organic semiconductors. Twisted and nonplanar molecular architectures are found to promote amorphous morphologies while maintaining local π-stacking. A graph theoretical network analysis demonstrates that these twisted molecules are more likely to form percolating three-dimensional pathways for charge motion than strictly planar molecules, which show connectivity in only one dimension.
AB - Large, twisted, and fused conjugated molecular architectures have begun to appear more prominently in the organic semiconductor literature. From a modeling perspective, such structures present a challenge to conventional simulation techniques; atomistic resolutions are computationally inefficient, while traditional isotropic coarse-grained models do not capture the inherent anisotropies of the molecules. In this work, we develop a simple coarse-grained model that explicitly incorporates the anisotropy of these molecular architectures, thereby providing a route toward analyzing π-stacking, and thus qualitative electronic structure, at a computationally efficient coarse-grained resolution. Our simple coarse-grained model maintains relative orientations of conjugated rings, as well as inter-ring dihedrals, that are critical for understanding electronic and excitonic transport in bulk systems. We apply this model to understand structural correlations in several recently synthesized perylene diimide (PDI)-based organic semiconductors. Twisted and nonplanar molecular architectures are found to promote amorphous morphologies while maintaining local π-stacking. A graph theoretical network analysis demonstrates that these twisted molecules are more likely to form percolating three-dimensional pathways for charge motion than strictly planar molecules, which show connectivity in only one dimension.
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U2 - 10.1021/acs.jctc.8b00742
DO - 10.1021/acs.jctc.8b00742
M3 - Article
C2 - 30407817
AN - SCOPUS:85057566838
SN - 1549-9618
VL - 14
SP - 6495
EP - 6504
JO - Journal of Chemical Theory and Computation
JF - Journal of Chemical Theory and Computation
IS - 12
ER -