Theory for Spectral Shape of Optical Absorption in Halogen-Bridged Mixed-Valent Metal Complexes

Abstract

Spectral shapes of optical absorptions in the charge density wave states of halogen-bridged mixed-valent metal complexes are theoretically determined for the first time, using a one-dimensional extended Peierls-Hubbard model. Two important effects beyond the mean field theory are taken into account; the electron-hole (e-h) correlation on the metal atoms, and the classical fluctuation of the halogen sublattice coordinates. It is shown that the exciton strongly affects the spectral shape of the charge transfer (CT) band. When the e-h binding is weak, the CT band is the mixture of the exciton absorption and the interband ones. When it is strong, on the other hand, the exciton dominates over all the CT band and, consequently, its higher energy side becomes very close to a Lorentzian. From the comparison with experimental data, it is concluded that platinum complexes correspond to strong binding cases. The intragap absorptions associated with nonlinear excitations such as solitons and polarons are also studied...