Calibrating transition metal energy levels and oxygen bands in first principles calculations: accurate prediction of redox potentials and charge transfer in lithium transition metal oxides

TL;DR

This paper introduces a first-principles computational method using an optimized hybrid functional to accurately predict electronic structures and redox potentials in transition metal oxides, crucial for energy applications.

Contribution

It develops a system-specific calibration of the HSE06 hybrid functional for better electronic structure predictions in TM oxides, improving upon existing methods.

Findings

Optimized HSE06 functional improves electronic density of states and energetics.

Band gaps increase linearly with the mixing parameter, enabling calibration.

G0W0@GGA+U band gaps match experimental data.

Abstract

Transition metal (TM) oxides play an increasingly important role in technology today including applications such as catalysis, solar energy harvesting, and energy storage. In many of these applications, the details of their electronic structure near the Fermi level are critically important for their properties. We propose a first-principles based computational methodology for the accurate prediction of oxygen charge transfer in TM oxides and lithium TM (Li-TM) oxides. To obtain accurate electronic structures, the Heyd-Scuseria-Ernzerhof (HSE06) hybrid functional is adopted and the amount of exact Hartree-Fock exchange (mixing parameter) is adjusted to reproduce reference band gaps. We show that the HSE06 functional with optimal mixing parameter yields not only improved electronic densities of states but also better energetics (Li-intercalation voltages) for LiCoO2 and LiNiO2 as compared to GGA, GGA+U and standard HSE06. We find that the optimal mixing parameters for TM oxides are system-specific and correlate with the covalency (ionicity) of the TM species. Strong covalent (ionic) nature of TM-O bonding leads to lower (higher) optimal mixing parameters. We find that optimized HSE06 functionals predict stronger hybridization of the Co 3d and O 2p orbitals than GGA, resulting in a greater contribution from oxygen states to charge compensation upon delithiation in LiCoO2. We also find that the band gaps of Li-TM oxides increase linearly with the mixing parameter, enabling the straightforward determination of optimal mixing parameters based on GGA ({\alpha} = 0.0) and HSE06 ({\alpha} = 0.25) calculations. Our results also show that G0W0@GGA+U band gaps of TM oxides (MO, M = Mn, Co, Ni) and LiCoO2 agree well with experimental references, suggesting that G0W0 calculations can be used as a reference for the calibration of the mixing parameter in case no experimental band gap has been reported.