Impact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors
Permanent link to this recordhttp://hdl.handle.net/10754/610559
MetadataShow full item record
AbstractThe polarizable environment surrounding charge carriers in organic semiconductors impacts the efficiency of the charge transport process. Here, we consider two representative organic semiconductors, tetracene and rubrene, and evaluate their polarization energies in the bulk and at the organic-vacuum interface using a polarizable force field that accounts for induced-dipole and quadrupole interactions. Though both oligoacenes pack in a herringbone motif, the tetraphenyl substituents on the tetracene backbone of rubrene alter greatly the nature of the packing. The resulting change in relative orientations of neighboring molecules is found to reduce the bulk polarization energy of holes in rubrene by some 0.3 eV when compared to tetracene. The consideration of model organic-vacuum interfaces highlights the significant variation in the electrostatic environment for a charge carrier at a surface although the net change in polarization energy is small; interestingly, the environment of a charge even just one layer removed from the surface can be viewed already as representative of the bulk. Overall, it is found that in these herringbone-type layered crystals the polarization energy has a much stronger dependence on the intralayer packing density than interlayer packing density.
CitationImpact of Molecular Orientation and Packing Density on Electronic Polarization in the Bulk and at Surfaces of Organic Semiconductors 2016 ACS Applied Materials & Interfaces
SponsorsThis work has been supported by King Abdullah University of Science and Technology (KAUST), the KAUST Competitive Research Grant program, and the Office of Naval Research Global (Award N62909-15-1-2003). We acknowledge the IT Research Computing Team and Supercomputing Laboratory at KAUST for providing computational and storage resources. This work has also used the computing resources of the Garnet, Spirit, and Copper supercomputing systems through the DoD HPCMP. We thank Professor Dan Frisbie for most stimulating discussions and Professor Jay Ponder for invaluable assistance in troubleshooting the Tinker suite. C.R. thanks the University of Kentucky Vice President of Research for start-up funds.
PublisherAmerican Chemical Society (ACS)
- Electrostatic Polarization Energies of Charge Carriers in Organic Molecular Crystals: A Comparative Study with Explicit State-Specific Atomic Polarizability Based AMOEBA Force Field and Implicit Solvent Method.
- Authors: Xu T, Wang W, Yin S
- Issue date: 2018 Jul 10
- Exploring the energy landscape of the charge transport levels in organic semiconductors at the molecular scale.
- Authors: Cornil J, Verlaak S, Martinelli N, Mityashin A, Olivier Y, Van Regemorter T, D'Avino G, Muccioli L, Zannoni C, Castet F, Beljonne D, Heremans P
- Issue date: 2013 Feb 19
- Polarization Energies at Organic-Organic Interfaces: Impact on the Charge Separation Barrier at Donor-Acceptor Interfaces in Organic Solar Cells.
- Authors: Ryno SM, Fu YT, Risko C, Brédas JL
- Issue date: 2016 Jun 22
- Quantitative analysis of intermolecular interactions in orthorhombic rubrene.
- Authors: Hathwar VR, Sist M, Jørgensen MR, Mamakhel AH, Wang X, Hoffmann CM, Sugimoto K, Overgaard J, Iversen BB
- Issue date: 2015 Sep 1
- Accurate calculation of transport properties for organic molecular semiconductors with spin-component scaled MP2 and modern density functional theory methods.
- Authors: Sancho-García JC, Pérez-Jiménez AJ
- Issue date: 2008 Jul 14