Disproportionation and electronic phase separation in parent manganite LaMnO_3

TL;DR

This paper investigates the anomalous high-temperature phase of LaMnO_3, proposing it as an electron-hole Bose liquid resulting from charge transfer instabilities, which explains various puzzling properties and phase separations.

Contribution

It introduces the concept of an electron-hole Bose liquid phase in LaMnO_3, explaining charge transfer instabilities and phase separation phenomena not accounted for in previous models.

Findings

Identification of a high-temperature EHBL phase in LaMnO_3.

Reproduction of temperature-dependent phase volume fractions.

Explanation of phase separation induced by external perturbations.

Abstract

Nominally pure undoped parent manganite LaMnO_3 exhibits a puzzling behavior inconsistent with a simple picture of an A-type antiferromagnetic insulator (A-AFI) with a cooperative Jahn-Teller ordering. We do assign its anomalous properties to charge transfer instabilities and competition between insulating A-AFI phase and metallic-like dynamically disproportionated phase formally separated by a first-order phase transition at T_{disp}=T_{JT}\approx 750 K. The unconventional high-temperature phase is addressed to be a specific electron-hole Bose liquid (EHBL) rather than a simple "chemically" disproportionated R(Mn^{2+}Mn^{4+})O_3 phase. New phase does nucleate as a result of the charge transfer (CT) instability and evolves from the self-trapped CT excitons, or specific EH-dimers, which seem to be a precursor of both insulating and metallic-like ferromagnetic phases observed in manganites. We arrive at highly frustrated system of triplet (e_g^2)^3A_{2g} bosons moving in a lattice formed by hole Mn^{4+} centers. Starting with different experimental data we have reproduced a typical temperature dependence of the volume fraction of high-temperature mixed-valent EHBL phase. We argue that a slight nonisovalent substitution, photo-irradiation, external pressure or magnetic field gives rise to an electronic phase separation with a nucleation or an overgrowth of EH-droplets. Such a scenario provides a comprehensive explanation of numerous puzzling properties observed in parent and nonisovalently doped manganite LaMnO_3 including an intriguing manifestation of superconducting fluctuations.