Charge Transfer Excitations in Insulating Copper Oxides

TL;DR

This paper develops a semi-quantitative model for charge transfer excitations in insulating cuprates, explaining optical and EELS spectra across various dimensionalities and revealing the momentum-dependent behavior of excitons.

Contribution

It generalizes the Zhang-Ng model by including complete orbital sets and exciton types, providing a unified description of spectra in different cuprates.

Findings

Charge transfer gap is set by localized and inter-center excitons.

EELS intensity sharply decreases near the Brillouin zone boundary.

Interaction of excitons can cause destructive interference effects.

Abstract

A semi-quantitative cluster approach is developed to describe the charge transfer (CT) electron-hole excitations in insulating cuprates in a rather wide energy range up to 10- 15 eV. It generalizes the Zhang-Ng (ZN) model of CT excitons by considering the complete set of Cu3d and O2p orbitals within the CuO4 embedded molecular cluster method and by introducing one-center (intra-center) Frenkel-like and two-center (inter-center) excitons. Special attention is paid to the transition matrix element effects both in optical and electron energy loss spectra (EELS). In the latter case we obtain the momentum dependence of matrix elements both for intra-center and inter-center transitions. We are able to give a semi-quantitative description of the optical and EELS spectra for a large number of 0D (like CuB2O4), 1D (Sr2CuO3) and 2D (like Sr2CuO2Cl2) insulating cuprates in a unifying manner. By comparing our analysis with the experimental data we find that the CT gap in insulating cuprates is determined by nearly degenerate intra-center localized excitations and inter-center CT excitons. The corresponding EELS intensity is found to be strongly k-dependent: even for isolated exciton it sharply decreases by approaching the Brillouin zone (BZ) boundary. It is shown that the interaction of two-center excitons can result in destructive interference effects with an intensity compensation point.