Optical and electron-energy-loss studies of the monomeric and dimeric phases of decamethylferrocenium tetracyanoquinodimethanide, (DMeFc)(TCNQ)

Abstract

The optical properties of the two crystallographic phases of 1:1 decamethylferrocenium tetracyanoquinodimethanide, (DMeFc)(TCNQ), have been measured from 0.1 to 10 eV. One phase consists of isolated paramagnetic TCNQ anion monomers while the other contains isolated diamagnetic dimers. The spectrum of the monomeric phase exhibits a strong localized monomer exciton which is not normally observed in solid TCNQ salts, while the dimeric phase shows a charge-transfer excitation as well as a shifted local exciton. From the frequency-dependent conductivity of the dimeric phase the effective on-site Coulomb interaction and the transfer matrix element are measured to be 1.0 and 0.27 eV, respectively. The infrared absorption spectrum of the dimeric phase shows an unusual activity of the symmetric phonon modes due to the interaction of these modes with the radical electron, whereas in the monomeric phase only normally infrared active phonons are observed. In electron-energy-loss measurements an anomalous momentum dependence of the line shape of the monomeric exciton was observed. This result is attributed to a dielectric effect caused by the decrease in strength of local excitons with increasing momentum.