Pressure-induced phase transition in the electronic structure of palladium nitride

TL;DR

This study combines theoretical and experimental methods to investigate pressure-induced electronic and structural phase transitions in PdN2, revealing a first-order transition driven by electronic hybridization changes and associated with elastic instability.

Contribution

It demonstrates the importance of advanced exchange-correlation functionals in accurately modeling high-pressure behavior of PdN2 and uncovers the electronic origin of the phase transition.

Findings

HSE06 functional accurately predicts the EOS of PdN2

Band gap closes below 11 GPa, indicating a phase transition

Structural transformation involves a change in Pd-d and N-p hybridization

Abstract

We present a combined theoretical and experimental study of the electronic structure and equation of state (EOS) of crystalline PdN2. The compound forms above 58 GPa in the pyrite structure and is metastable down to 11 GPa. We show that the EOS cannot be accurately described within either the local density or generalized gradient approximations. The Heyd-Scuseria-Ernzerhof exchange-correlation functional (HSE06), however, provides very good agreement with experimental data. We explain the strong pressure dependence of the Raman intensities in terms of a similar dependence of the calculated band gap, which closes just below 11 GPa. At this pressure, the HSE06 functional predicts a first-order isostructural transition accompanied by a pronounced elastic instability of the longitudinal-acoustic branches that provides the mechanism for the experimentally observed decomposition. Using an extensive Wannier function analysis, we show that the structural transformation is driven by a phase transition of the electronic structure, which is manifested by a discontinuous change in the hybridization between Pd-d and N-p electrons as well as a conversion from single to triple bonded nitrogen dimers. We argue for the possible existence of a critical point for the isostructural transition, at which massive fluctuations in both the electronic as well as the structural degrees of freedom are expected.