Microscopic analysis of the valence transition in tetragonal EuPd$_2$Si$_2$

TL;DR

This study uses ab initio DFT calculations to analyze the microscopic mechanisms behind the valence transition in EuPd₂Si₂, highlighting the role of electronic hybridization, structural changes, and the limits of theoretical modeling.

Contribution

It provides a detailed microscopic understanding of the valence transition in EuPd₂Si₂ through DFT analysis and comparison with experimental photoemission data.

Findings

Enhanced c-f hybridization during transition

Volume reduction correlates with electronic structure change

DFT results benchmarked against photoemission data

Abstract

Under temperature or pressure tuning, tetragonal EuPd$_2$Si$_2$ is known to undergo a valence transition from nearly divalent to nearly trivalent Eu accompanied by a volume reduction. Albeit intensive work, its microscopic origin is still being discussed. Here, we investigate the mechanism of the valence transition under volume compression by $ab~initio$ density functional theory (DFT) calculations. Our analysis of the electronic and magnetic properties of EuPd$_2$Si$_2$ when approaching the valence transition shows an enhanced $c$-$f$ hybridization between localized Eu 4$f$ states and itinerant conduction states (Eu 5$d$, Pd 4$d$, and Si 3$p$) where an electronic charge redistribution takes place. We observe that the change in the electronic structure is intimately related to the volume reduction where Eu-Pd(Si) bond lengths shorten and, for the transition to happen, we trace the delicate balance between electronic bandwidth, crystal field splitting, Coulomb repulsion, Hund's coupling and spin-orbit coupling. In a next step we compare and benchmark our DFT results to surface-sensitive photoemission data in which the mixed-valent properties of EuPd$_2$Si$_2$ are reflected in a simultaneous observation of divalent and trivalent signals from the Eu $4f$ shell. The study serves as well to explore the limits of density functional theory and the choice of exchange correlation functionals to describe such a phenomenon as a valence transition.