Orbital-selective charge transfer drives two-step negative thermal expansion structural transitions in PbTa2Se4

TL;DR

This study uncovers how orbital-selective charge transfer causes two-step negative thermal expansion structural transitions in PbTa2Se4, revealing new insights into NTE mechanisms and pressure-tuned superconductivity in this material.

Contribution

It demonstrates that orbital-selective charge transfer drives the unusual two-step NTE structural transitions in PbTa2Se4, combining experimental and theoretical approaches.

Findings

Charge transfer from Pb 6pz orbital during the first transition.

Modification of Fermi surface and orbitals in the second transition.

Pressure can tune structural phases and superconductivity.

Abstract

The negative thermal expansion (NTE) effect has been found generally combined with structural phase transitions. However, the charge and orbital freedoms of the NTE has not been well studied. This study employs angle-resolved photoemission spectroscopy and first-principles calculations to elucidate the charge and orbital kinetics of the anomalous two-step negative thermal expansion structural phase transitions in PbTa2Se4. As the temperature decreases, each transition undergoes a similar block-layer sliding, although the charge transfer behaviors differ significantly. During the first transition, charge is mainly transferred from the Pb 6pz orbital to an M-shaped band below the Fermi level, barely altering the Fermi surface. In contrast, the second transition involves modifications to both the Fermi surface and charge-transfer orbitals, with charge selectively transferred from Pb 6px/py orbitals to Ta 5dz2 orbitals and a decrease of the Fermi pockets formed by Pb 6px/py orbitals. Furthermore, a small pressure can easily tune the base structure phase among the three phases and the corresponding superconductivity. Therefore, our findings reveal that the orbital-selective charge transfer drives the unusual structure transition in PbTa2Se4, offering new insights into the NTE mechanisms and providing a unique window to study the pressure-tuned superconductivity in this metal-intercalated transition chalcogenides.