Systematic tight-binding analysis of ARPES spectra of transition-metal oxides

TL;DR

This paper systematically analyzes ARPES spectra of transition-metal oxides using tight-binding models, compares parameters with CI cluster-models, and discusses implications for electronic structure understanding.

Contribution

It provides a comprehensive tight-binding analysis of ARPES spectra for TM oxides and compares these parameters with CI and ab initio calculations, revealing insights into charge-transfer energies.

Findings

ARPES-derived $oldsymbol{ ext{d}- ext{p}}$ energy differences are similar to charge-transfer energies.

The $oldsymbol{ ext{d}- ext{p}}$ transfer integrals are consistent across methods.

Additional narrowing in ARPES spectra indicates effects beyond simple tight-binding models.

Abstract

We have performed systematic tight-binding (TB) analyses of the angle-resolved photoemission spectroscopy (ARPES) spectra of transition-metal (TM) oxides A$M$O$_3$ ($M=$ Ti, V, Mn, and Fe) with the perovskite-type structure and compared the obtained parameters with those obtained from configuration-interaction (CI) cluster-model analyses of photoemission spectra. The values of $\epsilon_d-\epsilon_p$ from ARPES are found to be similar to the charge-transfer energy $\Delta$ from O $2p$ orbitals to empty TM 3d orbitals and much larger than $\Delta-U/2$ ($U$: on-site Coulomb energy) expected for Mott-Hubbard-type compounds including SrVO$_3$. $\epsilon_d-\epsilon_p$ values from {\it ab initio} band-structure calculations show similar behaviors to those from ARPES. The values of the $p-d$ transfer integrals to describe the global electronic structure are found to be similar in all the estimates, whereas additional narrowing beyond the TB description occurs in the ARPES spectra of the $d$ band.