Abstract
For charge transport in organic semiconductors the geometrical response to the presence of the charge plays a crucial role. Often, charge transport in these materials can be considered as the hopping of a localized polaron. Unfortunately, the description of localized charge carriers within semilocal Density Functional Theory (DFT) is prevented by the self-interaction error that artificially delocalizes the charge. Here, we present a computational scheme for the description of localized charges in an organic semiconductor. Constrained DFT is used to localize the charge on one of the molecules of a molecular dimer. The availability of the forces from this constraint enables ab initio molecular dynamics calculations and gives access to the geometrical response of neighboring molecules to the presence of a charged neighbor. This is demonstrated for a pentacene dimer. The reorganization energy is found to increase from 91 meV to 108 meV when decreasing the distance between two Pentacene molecules from 7 Å to 4 Å.
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Franke, JH., Nair, N.N., Chi, L., Fuchs, H. (2012). Constrained Density Functional Theory of Molecular Dimers. In: Nagel, W., Kröner, D., Resch, M. (eds) High Performance Computing in Science and Engineering '11. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-23869-7_14
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DOI: https://doi.org/10.1007/978-3-642-23869-7_14
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-23868-0
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