Temperature induced in-gap states in the band structure and the insulator-metal transition in LaCoO3

TL;DR

This paper explains the temperature-induced spin-state transition and insulator-metal transition in LaCoO3 by calculating its temperature-dependent band structure using an advanced correlated electron method.

Contribution

It introduces a comprehensive theoretical approach that accounts for strong correlations, covalence, and spin-orbital interactions to explain LaCoO3's phase transitions.

Findings

Temperature-dependent band structure shows in-gap states.

Both spin-state and insulator-metal transitions are explained coherently.

Strong electron correlations are crucial for understanding LaCoO3's behavior.

Abstract

For many years a spin-state transition at $T \approx 100 K$ and insulator - metal transition (IMT) at $T_{IMT} \approx 600 K$ in LaCoO$_3 $ remains a mystery. Small low-spin - high-spin spin gap $\Delta _S = E\left( {HS} \right) - E\left( {LS} \right) \sim 100 K$ results in the spin-state transition. The large charge gap $2E_a \approx 2300 K$ ($E_a $ is the activation energy) vs. $\Delta _S $ and $T_{IMT} $ implies that LaCoO$_3 $ is not a simple narrow-gap semiconductor. Here we explain both the spin-state and IMT on the same footing. We obtain strong temperature dependent band structure in LaCoO$_3 $ by the LDA+GTB method that incorporates strong electron correlations, covalence and spin-orbital interaction exactly inside the CoO$_6 $ cluster and the interclaster hopping between different multielectron configurations by perturbation theory for Hubbard X-operators.