Anomalous lattice specific heat and rattling phonon modes in quadruple perovskites

TL;DR

This study investigates anomalous specific heat behaviors in quadruple perovskites, linking them to rattling phonon modes, confirmed by first-principles calculations and interpreted via a pseudo-Jahn-Teller effect.

Contribution

It provides experimental evidence of rattling phonon modes in quadruple perovskites and confirms their presence through DFT+U calculations, offering a new understanding of lattice dynamics.

Findings

Anomalous concave-down $C_p/T$ vs. $T^2$ curve observed

Bell-shaped feature in $eta(T)$ linked to rattling modes

First-principles calculations confirm rattling in Mn system

Abstract

Experimental data on the specific heat $C_p$ of quadruple perovskites ACu$_3$Fe$_2$Re$_2$O$_{12}$ (A = Mn, Cu, La, Ce, Dy) are presented, demonstrating an anomalous concave-down $C_p/T$ vs. $T^2$ curve and a bell-shaped feature in $\beta(T) = (C_p - \gamma T)/T^3$ plotted against $T$ on a logarithmic scale. This feature is most pronounced for A = Cu and Mn. These findings can be explained by the rattling phenomenon, previously identified in other systems such as filled skutterudites and $\beta$-pyrochlores. Using first-principles DFT+U calculations, the presence of a rattling mode in A = Mn system is directly confirmed. A qualitative interpretation of the rattling mechanism in terms of a pseudo-Jahn-Teller effect is proposed.