Influence of anti-ferromagnetic ordering and electron correlation on the electronic structure of MnTiO$_3$

TL;DR

This study combines experimental photoemission spectroscopy with advanced theoretical methods to elucidate how anti-ferromagnetic order and electron correlation influence the electronic structure of MnTiO₃, revealing the importance of electron correlation in its insulating state.

Contribution

It demonstrates that DFT+DMFT accurately describes the electronic structure of MnTiO₃ in both paramagnetic and anti-ferromagnetic phases, highlighting the role of electron correlation and magnetic ordering.

Findings

DFT(+$U$) predicts the AFM insulating ground state.

DFT+DMFT captures the paramagnetic phase properties accurately.

Electronic structure remains largely unchanged between AFM and PM phases in spectral function.

Abstract

Electron correlation and long-range magnetic ordering have a significant impact on the electronic structure and physical properties of solids. Here, we investigate the electronic structure of ilmenite MnTiO$_{3}$ using room temperature photoemission spectroscopy and theoretical approaches within density functional theory (DFT), DFT+$U$ and DFT+dynamical mean field theory (DMFT). Mn 2$p$ (Ti 2$p$) core level photoemission spectra, confirming Mn$^{2+}$ (Ti$^{4+}$) oxidation state, exhibit multiple satellites which are very similar to that of MnO (TiO$_{2}$), suggesting similar strength of various interactions in this system. Valence band spectra collected at different photon energies suggest dominant Mn 3$d$ character in the highest occupied band with a wide insulating gap. DFT(+$U$) correctly predicts the experimentally observed anti-ferromagnetic (AFM) insulating ground state for MnTiO$_3$ where the requirement of a large $U$ to reproduce the experimental values of magnetic moment and band gap signifies the importance of electron correlation. Magnetically disordered paramagnetic (PM) phase could be well captured within DFT+DMFT, which provides an excellent agreement for the experimental band gap, paramagnetic moment, valence band spectra as well as dominant Mn 3$d$ character in the highest occupied band. The calculated spectral function remains largely unaffected and exhibits sharper features in the magnetically ordered AFM phase. We show that the electronic structure of MnTiO$_{3}$ in both the PM and AFM phases can be accurately described within DFT+DMFT.