Unified understanding of the valence transition in the rare-earth monochalcogenides under pressure

Abstract

Valence instability is a key ingredient of the unusual properties of $f$ electron materials, yet a clear understanding is lacking as it involves a complex interplay between $f$ electrons and conduction states. Here we propose a unified picture of pressure-induced valence transition in Sm and Yb monochalcogenides, considered as a model system for mixed valent $4f$-electron materials. Using high-resolution x-ray-absorption spectroscopy, we show that the valence transition is driven by the promotion of a $4f$ electron specifically into the lowest unoccupied (LU) $5d$ ${t}_{2g}$ band. We demonstrate with a promotional model that the nature of the transition at low pressures is intimately related to the density of states of the LU band, while at high pressures it is governed by the hybridization strength.