DFT+ U and quantum Monte Carlo study of electronic and optical properties of AgNiO 2 and AgNi 1- x Co x O 2 delafossite

• Published in: Physical chemistry chemical physics : PCCP 2024-02, Vol.26 (8), p.6967-6976
• Main Authors: Shin, Hyeondeok, Ganesh, Panchapakesan, Kent, Paul R C, Benali, Anouar, Bhattacharya, Anand, Lee, Ho Nyung, Heinonen, Olle, Krogel, Jaron T
• Format: Article
• Language: English
• Subjects: INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
• ISSN: 1463-9076; 1463-9084
• DOI: 10.1039/D3CP03477A

As the only semimetallic d -based delafossite, AgNiO has received a great deal of attention due to both its unique semimetallicity and its antiferromagnetism in the NiO layer that is coupled with a lattice distortion. In contrast, other delafossites such as AgCoO are insulating. Here we study how the electronic structure of AgNi Co O alloys vary with Ni/Co concentration, in order to investigate the electronic properties and phase stability of the intermetallics. While the electronic and magnetic structure of delafossites have been studied using density functional theory (DFT), earlier studies have not included corrections for strong on-site Coulomb interactions. In order to treat these interactions accurately, in this study we use Quantum Monte Carlo (QMC) simulations to obtain accurate estimates for the electronic and magnetic properties of AgNiO . By comparison to DFT results we show that these electron correlations are critical to account for. We show that Co doping on the magnetic Ni sites results in a metal-insulator transition near ∼0.33, and reentrant behavior near ∼ 0.66.