Polarization in organic molecular crystals and charge-transfer salts

Abstract

Polarization in insulators is a general phenomenon that extends over nanometer distances. Two special cases illustrate recent theoretical progress. Polarization energies of localized charges in organic molecular crystals exceed the bandwidth and redistribute the charge density. A systematic treatment of electronic polarization is summarized in the limit of zero intermolecular overlap for pentacene crystals or thin films on metallic substrates, with special attention to the transport gap for producing a separated electron–hole pair and the optical dielectric tensor of the crystal. When overlap cannot be neglected, the general formulation of polarization in extended insulators is in terms of the exact ground state's phase. This formulation is applied to organic charge-transfer (CT) salts whose correlated electronic structure is described by one-dimensional Peierls–Hubbard models. Near the Peierls instability, coupling to lattice modes generates large peaks in the dielectric response that is primarily due to lattice vibrations. Comparisons with experiment are mentioned for both organic molecular crystals and CT salts.