DFT+DMFT study on pressure-induced valence instability of CeCoSi

TL;DR

This study uses DFT+DMFT calculations to explore how pressure induces valence changes in CeCoSi, linking electronic structure evolution to structural phase transitions and providing insights into the behavior of Ce-4f electrons under high pressure.

Contribution

The paper demonstrates the application of DFT+DMFT to accurately model pressure-induced valence instability and structural transitions in CeCoSi, highlighting the role of Ce-4f electron delocalization.

Findings

CeCoSi transitions to a mixed-valence state at ~5.5 GPa.

Pressure increases the hybridization strength of Ce-4f electrons.

Valence instability of Ce-4f electrons causes structural phase transition.

Abstract

Rare-earth compounds RCoSi exhibit unique properties, with distinct structural behaviors depending on whether R is a light, middle or heavy rare-earth element. Among them, CeCoSi undergoes a structural phase transition under high pressure, with the phase transition pressure increasing as temperature rises. Some experimental studies suggest that the transition is closely related to the behavior of Ce-4f electrons. In this work, we systematically studied the evolution of the electronic structure of CeCoSi with temperature and pressure. First, we used the DFT+DMFT to calculate the energy-volume curve of CeCoSi, which was in good agreement with the experimental results and far superior to the DFT method. Next, we studied the electronic structure of CeCoSi under different pressures and temperatures using DFT+DMFT. Our results show that CeCoSi is a Kondo metal with hybridization of Ce-4f and Co-3d. As pressure increases, the renormalization factor Z of Ce-4f5/2 increases, the occupancy number of Ce-4f electrons decreases, and CeCoSi transitions to a mixed-valence state at ~5.5 GPa in 100 K. The pressure of the quantum phase transition PQ is slightly higher than the experimentally observed structural phase transition pressure PS, and the PQ increases with increasing temperature, which is consistent with the behavior of PS in experiment. In addition, the hybridization strength of Ce-4f in the mixed-valence state is significantly greater than in the Kondo metal state. Our results suggest that the valence instability of Ce-4f is the cause of the structural phase transition. As pressure increases, Ce-4f electrons delocalize and CeCoSi transitions to mixed-valence state. This valence instability may cause redistribution of electron density, thus inducing a structural phase transition. Our work reveals the cause of the structural phase transition of CeCoSi under high pressure.