Polarization energies, transport gap and charge transfer states of organic molecular crystals

Abstract

AbstractA self‐consistent calculation of electronic polarization in organic molecular crystals and thin films is presented in terms of charge redistribution in nonoverlapping molecules in a lattice. The polarization energies P+ and P− of a molecular cation and anion are found for anthracene and perelynetetracarboxylic dianhydride (PTCDA), together with binding energies of ion pairs and transport gaps of PTCDA films on metallic substrates. The 500 meV variation of P++P− with film thickness agrees with experiment, as do calculated dielectric tensors. Comparisons are made to submolecular calculations in crystals.