A Dynamic Coupling Model of Optical Conductivity in Mixed-Valence Systems

TL;DR

This paper develops a theoretical model using Linear Response Theory to calculate optical conductivity in mixed-valence systems, revealing how absorption profiles relate to conductivity and the role of charge transfer bands.

Contribution

It introduces a comprehensive approach to compute optical conductivity in all three classes of mixed-valence systems based on absorption profiles.

Findings

Optical conductivity profiles resemble absorption profiles in shape and polarization.

Peaks in conductivity tend to shift to higher frequencies compared to absorption.

Charge transfer bands are the main contributors to optical conductivity.

Abstract

Using Linear Response Theory, with appropriate wave functions and energies from perturbation method, the absorption profiles can be calculated for all three classes of mixed-valence systems as defined by Robin and Day : Class III (delocalized), Class I (localized) and Class II (intermediate between III and I). Based on these absorption profiles, one can calculate the corresponding frequency-dependent optical conductivity profiles with the following results: For all three classes, the optical conductivity profiles are similar to their corresponding absorption profiles in regard to band shape and polarization, except peaks of these profiles tend to shift toward higher frequency with respect to the absorption profiles. The charge transfer absorption (CT band) is the major contributors of optical conductivity. Moreover, the CT-induced IR band, also contributes to optical conductivity, as it borrows its intensity from the CT band and the amount of borrowing depends on its proximity to the latter, as in Class II.