Interplay of p-d and d-d charge transfer transitions in rare-earth perovskite manganites

TL;DR

This study combines theoretical modeling and experimental ellipsometry to analyze optical charge transfer transitions in RMnO_3 manganites, revealing a dual nature of the optical gap involving p-d and d-d transitions.

Contribution

It provides a combined theoretical and experimental analysis of optical transitions in RMnO_3, clarifying the nature of the optical gap and challenging traditional insulator classifications.

Findings

Optical spectra agree with p-d and d-d charge transfer transition models.

The optical gap has a dual nature, involving forbidden p-d and inter-site d-d transitions.

RMnO_3 manganites do not fit neatly into CT or Mott-Hubbard insulator categories.

Abstract

We have performed both theoretical and experimental study of optical response of parent perovskite manganites RMnO_3 with a main goal to elucidate nature of clearly visible optical features. Starting with a simple cluster model approach we addressed the both one-center (p-d) and two-center (d-d) charge transfer (CT) transitions, their polarization properties, the role played by structural parameters, orbital mixing, and spin degree of freedom. Optical complex dielectric function of single crystalline samples of RMnO_3 (R=La, Pr, Nd, Sm, Eu) was measured by ellipsometric technique at room temperature in the spectral range from 1.0 to 5.0 eV for two light polarizations: E \parallel c and E \perp c. The comparative analysis of the spectral behavior of \varepsilon _1 and \varepsilon _2 is believed to provide a more reliable assignment of spectral features. We have found an overall agreement between experimental spectra and theoretical predictions based on the theory of one-center p-d CT transitions and inter-site d-d CT transitions. Our experimental data and theoretical analysis evidence a dual nature of the dielectric gap in nominally stoichiometric matrix of perovskite manganites RMnO_3, it is formed by a superposition of forbidden or weak dipole allowed p-d CT transitions and inter-site d-d CT transitions. In fact, the parent perovskite manganites RMnO_3 should rather be sorted neither into the CT insulator nor the Mott-Hubbard insulator in the Zaanen, Sawatzky, Allen scheme.