Lanthanide Oxides: From Diatomics to High-Spin, Strongly Correlated Homo- and Heterometallic Clusters

Abstract

Small lanthanide (Ln) oxide clusters present both experimental and theoretical challenges because of their partially filled, core-like 4f n orbitals, a feature that results in a plethora of close-lying and fundamentally similar electronic states. These clusters provide a bottom-up approach toward understanding the electronic structure of defective or doped bulk material but also can offer a challenge to the theorists to find a method robust enough to capture electronic structure patterns that emerge from within the 4f n (0 < n < 14) series. In this Feature Article, we explore the electronic structures of small lanthanide oxide clusters that deviate from bulk stoichiometry using anion photoelectron spectroscopy and supporting density functional theory calculations. We will describe the evolution of electronic structure with oxidation and how Ln x O y − cluster reactivities can be correlated with specific Ln-local orbital occupancies. These strongly correlated systems offer additional insights into how interactions between electrons and electronically complex neutrals can lead to detachment transitions that lie outside of the sudden one-electron detachment approximation generally assumed in anion photoelectron spectroscopy. With a better understanding of how we can control nominally forbidden transitions to sample an array of spin states, we suggest that more in-depth studies on the magnetic states of these systems can be explored. Extending these studies to other Ln-based materials with hidden magnetic phases, along with sequentially ligated single molecule magnets, could advance current understanding of these systems.

Assessing the performance of ΔSCF and the diagonal second-order self-energy approximation for calculating vertical core excitation energies

“…Historically, the ∆SCF approach with Hartree-Fock (HF) had been employed in the computation of ionization energies. [25][26][27][28] In recent years, ∆SCF has been used in conjunction with maximum overlap methods for computing core excitation energies and core binding energies due to the simplicity of separately optimizing the MOs of two reference states. 29,30 For weakly correlated systems, SCF determinants are often a good approximation for the ground electronic state.…”