5 research outputs found
Electronic polarization in pentacene crystals and thin films
Electronic polarization is evaluated in pentacene crystals and in thin films
on a metallic substrate using a self-consistent method for computing charge
redistribution in non-overlapping molecules. The optical dielectric constant
and its principal axes are reported for a neutral crystal. The polarization
energies P+ and P- of a cation and anion at infinite separation are found for
both molecules in the crystal's unit cell in the bulk, at the surface, and at
the organic-metal interface of a film of N molecular layers. We find that a
single pentacene layer with herring-bone packing provides a screening
environment approaching the bulk. The polarization contribution to the
transport gap P=(P+)+(P-), which is 2.01 eV in the bulk, decreases and
increases by only ~ 10% at surfaces and interfaces, respectively. We also
compute the polarization energy of charge-transfer (CT) states with fixed
separation between anion and cation, and compare to electroabsorption data and
to submolecular calculations. Electronic polarization of ~ 1 eV per charge has
a major role for transport in organic molecular systems with limited overlap.Comment: 10 revtex pages, 6 PS figures embedde