[Paper Review] Pressure induced redistribution of oxygen hole states in La$_{4}$Ni$_{3}$O$_{10}$

Guiwen Jiang, Liang Si+2 more|arXiv (Cornell University)|Mar 14, 2026

Chemical and Physical Properties of Materials0 citations

TL;DR

This paper uses DFT and multi-orbital cluster exact diagonalization to show how pressure redistributes oxygen hole states in La4Ni3O10, switching from a central-layer Zhang-Rice singlet and interlayer 3-spin-polaron at ambient pressure to hole localization on outer layers forming in-plane Zhang-Rice singlets and a shared interlayer 3-spin-polaron under high pressure.

ABSTRACT

Using density functional calculations and multi-orbital, multi-atom cluster exact diagonalization that includes local exchange and Coulomb interactions, we explored the local low-energy electronic states of trilayer La$_4$Ni$_3$O$_{10}$ via a minimal Ni$_3$O$_{14}$ cluster. We find that, at ambient pressure, starting with all three Ni being nominally 2+ valence, one of the two extra holes is localized in the central NiO$_2$ layer forming a Zhang-Rice singlet (ZRS) with $d_{x^2-y^2}$ orbital. The other hole mainly occupies the antibonding combination of the two interplane O $p_z$ orbitals and thereby hybridizes with an out-of-plane three-spin-polaron (3SP) formed by the $d_{z^2}$ orbitals of three NiO$_2$ layers. In this way, the in-plane spin orientation alternation is carried by the $d_{x^2-y^2}$ orbitals of two outer layers with interlayer antiferromagnetic correlation. Simultaneously, the central layer is insulating with negligible magnetic moment. At high pressure, however, the two extra holes are concentrated on one of two outer layers and the inner layer separately forming the ZRS with $d_{x^2-y^2}$ orbitals or in-plane 3SP with neighboring cluster. We highlight the similarities between the bilayer La$_3$Ni$_2$O$_7$ and trilayer La$_4$Ni$_3$O$_{10}$ via possible charge and spin ordered states suggested by our cluster results.

Motivation & Objective

• Motivate understanding of how pressure alters electronic and magnetic states in trilayer nickelates.
• Identify the local low-energy states and hole distribution in La4Ni3O10 using a minimal Ni3O14 cluster.
• Determine how pressure changes hole localization among Ni d and O p orbitals and the resulting spin correlations.
• Compare ambient and high-pressure electronic configurations to relate to observed superconductivity trends.

Proposed method

• Perform DFT calculations to obtain structural and electronic parameters and Wannier projections for Ni d and O p states.
• Construct a multi-orbital Ni3O14 cluster model including Ni d_{x2-y2}, Ni d_{z2}, in-plane O p, and interlayer O p_z orbitals.
• Include on-site Coulomb interactions via Racah parameters (A,B,C) and Hund's coupling.
• Solve the cluster Hamiltonian exactly by diagonalization to obtain ground and low-lying excited states as a function of t_pd and t_dO.
• Vary hybridizations to simulate pressure effects while keeping the t_pd/t_dO ratio fixed to track phase transitions.

Experimental results

Research questions

• RQ1 How are the extra holes distributed among Ni d and O p orbitals in La4Ni3O10 at ambient pressure?
• RQ2 How does pressure reallocate holes between the central and outer NiO2 layers?
• RQ3 What are the resulting spin and magnetic correlations associated with the redistributed holes under different pressures?
• RQ4 Can the trilayer cluster results be connected to known bilayer nickelate physics and superconductivity trends?

Key findings

• Ambient pressure: one hole forms a central-layer Zhang-Rice singlet with d_{x2-y2}, the other hole resides on the antibonding interlayer O p_z combination and couples to a 3-spin-polaron formed by three d_{z2} orbitals.
• Under high pressure: the two extra holes concentrate on outer layers, forming in-plane Zhang-Rice singlets or in-plane 3-spin-polaron states, with the central layer also hosting a d_{x2-y2} hole.
• The central layer becomes insulating with negligible magnetic moment at ambient pressure, while outer-layer antiferromagnetic correlations are present between layers.
• The interlayer apical O p_z holes hybridize with z orbitals to form a 3-spin-polaron that couples across layers, with pressure driving a transition to a configuration where holes occupy in-plane O states on outer layers.
• The study highlights similarities to La3Ni2O7 physics, suggesting possible charge/spin-ordered states and related superconducting tendencies under pressure.